CN107531920A - Polycarbonate resin film - Google Patents

Abstract

The problem of the present invention is, passes through the polycarbonate resin containing specific polycarbonate resin Yu specific ultra-violet absorber, there is provided：The film of the specific ultraviolet of absorption do not have roller to pollute, oozed out.The present invention relates to a kind of polycarbonate resin film, and it is the polycarbonate resin film formed by poly carbonate resin composition, and the poly carbonate resin composition contains：The parts by weight of polycarbonate resin 100 comprising the construction unit from the dihydroxy compounds shown in following formula (1)；With, it more than the fusing point below 0.45 parts by weight and 7 parts by weight is 135 DEG C of ultra-violet absorbers for being higher than less than 300 DEG C and 5% weightless temperature 240 DEG C to be relative to the parts by weight of polycarbonate resin 100, and the wavelength 380nm of polycarbonate resin film light transmittance is more than 0.001% and less than 15% and thickness is 5 μm~120 μm.

Description

Polycarbonate resin film

Technical field

Protected the present invention relates to the polycarbonate resin film formed by poly carbonate resin composition, using its polarisation part Protect film and poly carbonate resin composition.

Background technology

In the past, as obtaining the method for polycarbonate resin, it is proposed that following method：With obtained by biomass resource two Hydroxy compounds is that isobide (following, brief note makees ISB sometimes) is monomer component, passes through the ester exchange with carbonic diester, side The monohydroxy compound of by-product is distilled into removal under reduced pressure, while obtain polycarbonate resin (referring for example to patent document 1~ 4).In addition, also studied in addition to being utilized as the moulding material for having played heat resistance by the polycarbonate resin that ISB is obtained The excellent optical characteristics of performance, the utilization in optical thin film (referring for example to patent document 5).

In general polarisation part protective film adds ultra-violet absorber to protect polarisation part from ultraviolet.However, The amount of ultra-violet absorber is necessary for a large amount of, and the problems such as oozing out be present.In order to eliminate these, it is known to, addition and resin The high ultra-violet absorber of compatibility, have ultraviolet radiation absorption function polymer method (referring for example to patent document 6).

But in general, the water imbibition of the cellulose ester film used in polarisation part protective film is high, for large-scale electricity In the case of depending on grade, the problem of durability deficiency be present.In addition, it is also proposed that thin using the polarisation part protection of acrylic resin Film (referring for example to patent document 7), due to there is fragility, therefore, during operation occur to be broken and be difficult to filming sometimes.

In addition, in the case of display using in general Polarizer, across the light of Polarizer be rectilinearly polarized light, because This, when polarized sunglasses observe display, blackout occurs due to angle sometimes.In order to eliminate it, make polarisation part sometimes The top layer of protective film is phase-contrast film (referring for example to patent document 8).In these phase-contrast films, in order to protect polarisation part Also contain ultra-violet absorber from ultraviolet.

For example, in the case of using cyclic olefin polymer (following, sometimes brief note make COP), in order to prevent from oozing out, roller it is dirty Dye, there is following technology：Be 2 kinds 3 layers and contain ultra-violet absorber only in sandwich layer (referring for example to patent document 9).

Prior art literature

Patent document

Patent document 1：International Publication No. 2004/111106

Patent document 2：Japanese Laid-Open 2006-232897 publications

Patent document 3：Japanese Laid-Open 2006-28441 publications

Patent document 4：Japanese Laid-Open 2008-24919 publications

Patent document 5：Japanese Laid-Open 2011-021171 publications

Patent document 6：Japanese Laid-Open 2002-047357 publications

Patent document 7：Japanese Laid-Open 2013-83956 publications

Patent document 8：Japanese Laid-Open 2011-137954 publications

Patent document 9：Japanese Laid-Open 2015-31753 publications

The content of the invention

Problems to be solved by the invention

However, the polycarbonate resin obtained by ISB does not have ultraviolet radiation absorption substantially, therefore, protected for polarisation part thin During film, it is necessary to contain substantial amounts of ultra-violet absorber.On the other hand, polycarbonate resin contains substantial amounts of ultra-violet absorber When, there are the following problems：The heat resistance of film reduces, oozes out the film caused by material is muddy, from the thin of roller pollution etc. Bad order, the uniformity of film thickness of the films such as the foreign matter of film, gear line reduce etc..In addition, sometimes due to specificization Compound and produce roller pollution etc..

Therefore, it is an object of the present invention to eliminate these problems, using specific polycarbonate resin, containing specific Ultra-violet absorber, so as to provide：The muddiness for the film caused by material for do not have the heat resistance of film to reduce, oozing out, it is derived from The problems such as bad orders of film such as the foreign matter of film of roller pollution, gear line, there is uniform film thickness and absorb spy The polycarbonate resin film of fixed ultraviolet.

The solution used to solve the problem

The present inventor etc. further investigate, as a result found to solve above-mentioned problem repeatedly：Using comprising from following formula (1) polycarbonate resin of the construction unit of the dihydroxy compounds shown in, specific ultra-violet absorber is added, so as to carry For：There is no the heat resistance of film to reduce, the foreign matter of the muddiness of film caused by the material that oozes out, film from roller pollution, The film of the problems such as bad order of the films such as gear line, the specific ultraviolet of absorption high-quality, so far completes this hair It is bright.That is, idea of the invention is that following [1]~[6].

[1] a kind of polycarbonate resin film, it is that the polycarbonate resin formed by poly carbonate resin composition is thin Film, the poly carbonate resin composition contain：Include the construction unit from the dihydroxy compounds shown in following formula (1) The parts by weight of polycarbonate resin 100；With, relative to the parts by weight of polycarbonate resin 100 be more than 0.45 parts by weight and 7 parts by weight Following fusing point is 135 DEG C of ultra-violet absorbers for being higher than 240 DEG C less than 300 DEG C and 5% weightless temperature, described poly- The wavelength 380nm of carbonate resin film light transmittance is more than 0.001% and less than 15% and thickness is 5 μm~120 μm.

[2] polycarbonate resin film according to [1], wherein, following formula (3) institute in foregoing polycarbonates resin The content for the compound shown is more than 10 weight ppm and below 1200 weight ppm.

[3] according to the polycarbonate resin film described in [1] or [2], wherein, foregoing ultra-violet absorber be triazine system, Enumerate BTA system, quinolinone system, benzoxazole system or indoles system.

[4] according to the polycarbonate resin film any one of [1]~[3], phase difference is in the face at its 548nm More than 100nm and below 200nm.

[5] a kind of polarisation part protective film, it is to use the polycarbonate resin film any one of [1]~[4] Form.

[6] a kind of poly carbonate resin composition, it contains：Include the dihydroxy compounds shown in from following formula (1) Construction unit the parts by weight of polycarbonate resin 100；With, relative to the parts by weight of polycarbonate resin 100 be more than 0.45 weight The fusing point below part and 7 parts by weight is measured as 135 DEG C less than 300 DEG C and ultraviolet of 5% weightless temperature higher than 240 DEG C Absorbent, the content of the compound shown in following formula (3) in foregoing polycarbonates resin is more than 10 weight ppm and 1200 weights Measure below ppm.

The effect of invention

According to the present invention it is possible to provide：Although containing substantial amounts of ultra-violet absorber, film will not produce when being film Foreign matter, the gear line of the muddiness of film caused by the heat resistance reduction of raw film, the material oozed out, the film from roller pollution Deng film bad order the problems such as, the optical thin film of high performance is shown as polarisation part protective film.And then it will not produce Raw roller pollution, therefore, can significantly cut down the bad order product in shaping, so as to improve productivity ratio, workability and system The quality of product.

Embodiment

Hereinafter, embodiments of the present invention are described in detail, but it is following described in the explanation of feature be the present invention Embodiment one (typical example), as long as the present invention following content is just not limited to no more than its purport.

The polycarbonate resin film of the present invention is by the polycarbonate resin containing polycarbonate resin and ultra-violet absorber Oil/fat composition is formed.

[polycarbonate resin]

Poly carbonate resin composition in the present invention contains：Include the dihydroxy compounds shown in from following formula (1) Construction unit polycarbonate resin.

(the end group structure of polycarbonate resin)

Polycarbonate resin can be by making the polycondensation under melting of dihydroxy compounds and carbonic diester and catalyst Make.As carbonic diester, carbonic diester described later can be used.Wherein, preferably using diphenyl carbonate.

Now, the polycarbonate resin of manufacture, shown in following structural formula (2) end group (it is following, be denoted as sometimes " phenyl end ") presence number (A) relative to the ratio (A/B) of whole end numbers (B) be preferably 75% less than 98% Scope.

In addition, ratio (A/B) of the presence number (A) of the phenyl end of polycarbonate resin relative to whole end numbers (B) More preferably more than 76% scope, particularly preferably more than 77% scope.In addition, more preferably less than 96% scope, Particularly preferably less than 95% scope.

When the presence number (A) of phenyl end is less than 75% relative to the ratio (A/B) of whole end numbers (B), injection moulding When products formed in easily produce and be referred to as easily producing bubble in the bad order of filamentary silver, extrusion molding.In addition, phenyl end Exist number (A) relative to whole end numbers (B) ratio (A/B) be more than 98% when, have the outward appearance in injection moulding, extrusion molding The tendency of bad reduction.In addition, it is desirable to when obtaining the polycarbonate resin of (A/B) more than 98%, make polymerizing condition strict or need To react for a long time, as a result, cause the deterioration of polycarbonate resin, be only capable of accessing the possibility of product of hue difference very It is high.

The presence number (A) of the phenyl end of polycarbonate resin is adjusted relative to the ratio (A/B) of whole end numbers (B) It is not particularly limited for the method for above range.For example, by relative to the carbonic acid of the whole dihydroxy compounds used in reaction Diester amount with that can obtain the scope of desired HMW body than being adjusted, or section passes through that deaerate will after polymerization Residual monomer is removed to outside reaction system, or improves stirring efficiency of reaction machine in polymerisation back segment etc. to improve reaction Speed, it is possible thereby to which the presence number (A) of phenyl end is adjusted to above-mentioned model relative to the ratio (A/B) of whole end numbers (B) Enclose.

The ratio of phenyl end in polycarbonate resin can utilize NMR spectrometers, use addition TMS (tetramethylsilanes Alkane) as the deuterochloroform for determining solvent, utilize¹The measure of H-NMR spectrum and calculate.

It should be noted that the dihydroxy compounds of the bonding structure with structural formula (1) and ester ring type dihydroxy chemical combination The usage rate of thing and other dihydroxy compounds used as needed is according to from the poly- carbonic acid used in the composition present invention The ratio of the Component units of each dihydroxy compounds of ester resin and suitably adjust.

(content and content control method of the compound shown in formula (3))

Special oligomer shown in the following formula (3) of polycarbonate resin further preferably specified quantitative in the present invention into Point.

When its amount of above-claimed cpd is very few, in the fabrication stage of polycarbonate resin, heat or the reaction of surplus are consumed sometimes Holdup time is elongated, there is the possibility that the tone for causing polymer deteriorates.In addition, when excessive, generation device is dirty when being molded sometimes The problem of bad order of the problem of dye or generation products formed.Therefore, formula (3) institute in the polycarbonate resin in the present invention The content for the compound shown is preferably more than 10 weight ppm and below 1200 weight ppm.

In addition, the content of compound shown in formula (3) in the polycarbonate resin of the present invention is more preferably 15 weight ppm Above, particularly preferably more than 20 weight ppm.In addition, more preferably below 650 weight ppm, it is particularly preferably 400 weight ppm Below.The content of the compound shown in formula (3) in polycarbonate resin is if above range, then polluting, be smelly when being molded Gas disappears, and molded appearance is good, therefore it is preferred that.

For the content of the compound shown in adjustment type (3), it is preferred that in polycarbonate resin is made, make phenyl The presence number (A) of end is less than 98% relative to the ratio (A/B) of whole end numbers (B).

And then by making the pressure in final polymerization tank be below 1kPa or make the polymerization at a temperature of higher than 220 DEG C Time is less than 2 hours, so as to the generation of the compound shown in suppressed FCM (3).Particularly, by making the final polymerization tank be Horizontal reacting groove, so as to tremendous improve devolatilization efficiency.In addition, by being carried out in an extruder using vaccum exhaust outlet Implement water filling when devolatilization or devolatilization, so as to be specified quantitative by the compound control shown in formula (3).

Polycarbonate resin in the present invention is dihydroxy compounds is existed with carbonic diester with catalyst generally as be described hereinafter Obtained from the lower polycondensation of melting.In the polycondensation reaction, from carbonic diester to depart from the Form generation monohydroxy compound of composition.

For example, in the case of using diphenyl carbonate as carbonic diester, the monohydroxy compound of generation is phenol.This When, device pollution, foul smell when the content of the monohydroxy compound in generation gained polycarbonate resin is more sometimes and is molded The problem of.

As the higher limit of the content of the monohydroxy compound in the polycarbonate resin in the present invention, do not limit especially System, usually below 1200 weight ppm, be preferably below 650 weight ppm, particularly preferably below 500 weight ppm.Poly- carbonic acid During the manufacture of ester resin, using the appropriate specific phosphorus series compound as catalyst deactivation agent described later, further fully enter Row devolatilization is handled, and so as to reduce the content of the monohydroxy compound in polycarbonate resin, and suppresses the generation under heating. The details of the assay method of monohydroxy compound amount in polycarbonate resin, which is recorded in, to be implemented in item.

In addition, as lower limit, it is not particularly limited, usually more than 0.1 weight ppm, more preferably 1 weight More than ppm, particularly preferably more than 10 weight ppm.When they are very few, in purification phase, it is necessary to apply the heat of surplus or extend The holdup time is reacted, there is the possibility that the tone for causing polymer deteriorates, preferably above range.

[manufacture method of polycarbonate resin]

Hereinafter, the method for the polycarbonate resin in the manufacture present invention is described in detail.

＜ raw materials ＞

(dihydroxy compounds)

Polycarbonate resin in the present invention is to include the construction unit from the dihydroxy compounds shown in following formula (1) Polycarbonate resin.

In the present invention, polycarbonate resin is preferably, in the structure from the dihydroxy compounds shown in above-mentioned formula (1) On the basis of unit, as needed, comprising from selected from as shown in the dihydroxy compounds shown in following formula (4), following formula (5) Dihydroxy compounds, the dihydroxy compounds shown in following formula (6), the dihydroxy compounds shown in following formula (7) and following The construction unit of the dihydroxy compounds of one or more of the group of dihydroxy compounds composition shown in formula (8).

HO-R⁵-OH (5)

(in above-mentioned formula (5), R⁵Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20.)

HO-CH₂-R⁶-CH₂-OH (6)

(in above-mentioned formula (6), R⁶Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20.)

H-(O-R⁷)_p-OH (7)

(in above-mentioned formula (7), R⁷The substituted or unsubstituted alkylidene of carbon number 2~10 is represented, p is 2~100 integer.)

HO-R⁸-OH (8)

(in above-mentioned formula (8), R⁸Represent the substituted or unsubstituted alkylidene of carbon number 2~20.)

It should be noted that in following, the carbon number of various groups refers in the case where the group has substituent, also wraps Include the carbon number of the total including the carbon number of the substituent.

(dihydroxy compounds shown in formula (1))

Polycarbonate resin in the present invention includes the construction unit for being derived from the dihydroxy compounds shown in above-mentioned formula (1).

As the dihydroxy compounds shown in above-mentioned formula (1), such as the different of the relation in stereoisomer can be enumerated The anhydrous sugar alcohols such as sorbierite, different mannitol, different iditol.They can be used alone, and can also combine two or more Use.In these dihydroxy compounds, from the easiness, optical characteristics, mouldability aspect for obtaining and manufacturing, most preferably , will exist as aboundresources, obtained by the D-sorbite dehydrating condensation that the various starch that can be readily available manufacture Isobide.

Polycarbonate resin is simultaneously comprising in addition to the construction unit from the dihydroxy compounds shown in above-mentioned formula (1) In the case of construction unit, its ratio is not particularly limited, and can suitably be set according to the requirement performance of polycarbonate resin.

(dihydroxy compounds shown in formula (4)~(8))

In the present invention, polycarbonate resin can include as needed：From selected from as the dihydroxy shown in above-mentioned formula (4) Shown in the dihydroxy compounds shown in dihydroxy compounds, above-mentioned formula (6), above-mentioned formula (7) shown in compound, above-mentioned formula (5) Dihydroxy compounds and above-mentioned formula (8) shown in dihydroxy compounds composition one or more of group dihydroxy compounds Construction unit.

(dihydroxy compounds shown in formula (4))

Dihydroxy compounds shown in above-mentioned formula (4) is that intramolecular has ring-type ether structure and is referred to as the spiroglycol Compound.

(dihydroxy compounds shown in formula (5))

Dihydroxy compounds shown in above-mentioned formula (5) is R⁵It is upper with carbon number 4~20, preferably the substitution of carbon number 4~18 or The ester ring type dihydroxy compounds of unsubstituted ring alkylidene.Herein, R⁵In the case of with substituent, as the substituent, The substituted or unsubstituted alkyl of carbon number 1~12 can be enumerated.In the case that the alkyl has substituent, as the substituent, Aryl such as the alkoxies such as methoxyl group, ethyoxyl, propoxyl group, phenyl, naphthyl etc. can be enumerated.

The dihydroxy compounds is by that with ring structure, can improve products formed when gained polycarbonate resin is molded Toughness, wherein toughness when being shaped to film can be improved.

As R⁵Ring alkylidene, as long as being just not particularly limited for the alkyl with ring structure, can be with end of the bridge Bridge crosslinking structure as carbon atom.From dihydroxy compounds easy to manufacture and from the viewpoint of impurity level being reduced, above-mentioned formula (5) dihydroxy compounds shown in be preferably the compound comprising five-membered ring structure or six-membered ring structure, i.e., preferably R⁵To take Generation or unsubstituted ring pentylidene or the dihydroxy compounds of substituted or unsubstituted cyclohexylene.If such dihydroxy Based compound, then by the way that the heat resistance of gained polycarbonate resin comprising five-membered ring structure or six-membered ring structure, can be improved.Should Six-membered ring structure can be fixed to chair shape or boat-shaped by covalent bond.

Wherein, the dihydroxy compounds shown in above-mentioned formula (5) is preferably R⁵For the various isomers shown in following formula (9). Herein, in formula (9), R¹¹Represent the substituted or unsubstituted alkyl of hydrogen atom or carbon number 1~12.R¹¹For the carbon with substituent In the case of the alkyl of number 1~12, as the substituent, can enumerate the alkoxies such as methoxyl group, ethyoxyl, propoxyl group, phenyl, Aryl such as naphthyl etc..

As the dihydroxy compounds shown in above-mentioned formula (5), more specifically, tetramethylcyclobutanediol, 2 can be enumerated, 2,4,4- tetramethyl -1,3- cyclobutanediols, 1,2- rings pentanediol, 1,3- rings pentanediol, 1,2- cyclohexanediols, 1,3- hexamethylenes two Alcohol, Isosorbide-5-Nitrae-cyclohexanediol, 2- methyl isophthalic acids, 4- cyclohexanediols, three ring decanediol classes, five rings glycols etc., but do not appointed by these What is limited.

They can be used singly or in combination of two or more.

(dihydroxy compounds shown in formula (6))

Dihydroxy compounds shown in above-mentioned formula (6) is R⁶It is upper with carbon number 4~20, preferably the substitution of carbon number 3~18 or The ester ring type dihydroxy compounds of unsubstituted ring alkylidene.Herein, R⁶In the case of with substituent, as the substituent, The substituted or unsubstituted alkyl of carbon number 1~12 can be enumerated.In the case that the alkyl has substituent, as the substituent, Aryl such as the alkoxies such as methoxyl group, ethyoxyl, propoxyl group, phenyl, naphthyl etc. can be enumerated.

The dihydroxy compounds is by that with ring structure, can improve products formed when gained polycarbonate resin is molded Toughness, it is particularly possible to improve toughness when being shaped to film.

As R⁶Ring alkylidene, as long as being just not particularly limited for the alkyl with ring structure, can be with end of the bridge Bridge crosslinking structure as carbon atom.From dihydroxy compounds easy to manufacture and from the viewpoint of impurity level being reduced, above-mentioned formula (6) dihydroxy compounds shown in be preferably the compound comprising five-membered ring structure or six-membered ring structure, i.e., preferably R⁶To take Generation or unsubstituted ring pentylidene or the dihydroxy compounds of substituted or unsubstituted cyclohexylene.

If such dihydroxy compounds, then by the way that comprising five-membered ring structure or six-membered ring structure, institute can be improved Obtain the heat resistance of polycarbonate resin.The six-membered ring structure can be fixed to chair shape or boat-shaped by covalent bond.Above-mentioned formula (6) in the dihydroxy compounds shown in, R⁶Various isomers shown in preferably above-mentioned formula (9).

As the dihydroxy compounds shown in above-mentioned formula (6), more specifically, can enumerate 1,2-CHDM, Double (hydroxymethyl) three ring [5.2.1.0 of 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol, 3,8-^2.6] decane, 3,9- be double (hydroxymethyl) three ring [5.2.1.0^2.6] decane, double (hydroxymethyl) three ring [5.2.1.0 of 4,8-^2.6] decane, the double (hydroxyls of 4,9- Methyl) three ring [5.2.1.0^2.6] decane etc., but not by these any restriction.

They can be used singly or in combination of two or more.That is, these dihydroxy compounds are for manufacture The reasons why upper, is obtained in the form of the mixture of isomers sometimes, at this time it is also possible to directly be made in the form of isomer mixture With.

Such as double (hydroxymethyl) three ring [5.2.1.0 of 3,8- can be used^2.6] decane, double (hydroxymethyl) three rings of 3,9- [5.2.1.0^2.6] decane, double (hydroxymethyl) three ring [5.2.1.0 of 4,8-^2.6] double (hydroxymethyl) three rings of decane and 4,9- [5.2.1.0^2.6] decane etc. mixture.

In the concrete example of dihydroxy compounds shown in above-mentioned formula (6), particularly preferred cyclohexanedimethanol class, from what is obtained From the viewpoint of easiness, the easiness of operation, preferably 1,4-CHDM, 1,3-CHDM, 1,2- hexamethylenes Alkane dimethanol.

(dihydroxy compounds shown in formula (7))

Dihydroxy compounds shown in above-mentioned formula (7) is R⁷It is upper that there is carbon number 2~10, the preferably substitution of carbon number 2~5 or nothing The compound of substituted alkylidene.P be 2~100 integer, be preferably 6~50 integer, more preferably 12~40 integer.

As the dihydroxy compounds shown in above-mentioned formula (7), it can specifically enumerate diethylene glycol, triethylene glycol, gather Ethylene glycol (molecular weight 150~4000) etc., but not by these any restriction.As the dihydroxy chemical combination shown in above-mentioned formula (7) Thing, the polyethylene glycol of preferred molecular weight 300~2000, the polyethylene glycol of wherein preferred molecular number 600~1500.

They can be used singly or in combination of two or more.

(dihydroxy compounds shown in formula (8))

In dihydroxy compounds shown in above-mentioned formula (8), R⁸Taken for carbon number 2~20, the preferably substitution of carbon number 2~10 or nothing The alkylidene in generation.R⁸The substituted base of alkylene group in the case of, as the substituent, the alkyl of carbon number 1~5 can be enumerated.

In dihydroxy compounds shown in above-mentioned formula (8), as R⁸For the substituted or unsubstituted alkylidene of carbon number 2~20 Dihydroxy compounds, specifically, ethylene glycol, propane diols, BDO, 1,6- hexylene glycols etc. can be enumerated, but not by These any restriction.

In these dihydroxy compounds, from the reactivity height when easiness obtained, the easiness of operation, polymerization, gained From the viewpoint of the form and aspect of polycarbonate resin, preferably 1,3-PD, 1,6- hexylene glycols.And go out from the viewpoint of heat resistance Hair, the preferably the spiroglycol with acetal ring.They can be used alone according to the requirement performance of gained polycarbonate resin, Two or more use can also be combined.

It should be noted that in the present invention, for polycarbonate resin, the dihydroxy shown in from above-mentioned formula (4) The construction unit of compound, the construction unit from the dihydroxy compounds shown in above-mentioned formula (5), from shown in above-mentioned formula (6) The construction unit of dihydroxy compounds, the construction unit from the dihydroxy compounds shown in above-mentioned formula (7) and from above-mentioned formula (8) in the construction unit of the dihydroxy compounds shown in, preferably comprise：From the dihydroxy compounds shown in above-mentioned formula (6) Construction unit and/or the construction unit from the dihydroxy compounds shown in above-mentioned formula (7).In addition, from reactivity, heat resistance, And then set out in terms of the decomposition of little in heat retention, more preferably include the knot for being derived from the dihydroxy compounds shown in above-mentioned formula (6) Structure unit.

(other dihydroxy compounds)

In the present invention, for polycarbonate resin, the dihydroxy that will can be derived from as needed shown in above-mentioned formula (4)~(8) The construction unit of based compound is replaced into the construction unit from other dihydroxy compounds.

As other dihydroxy compounds, such as bisphenols, oxirane (EO) the addition class of bisphenols, fluorenes can be enumerated Compound etc..

＜ bisphenols ＞

As bisphenols, for example, can enumerate double (4- hydroxy phenyls) propane (=bisphenol-A) of 2,2-, 2,2- it is double (4- hydroxyls- 3,5- 3,5-dimethylphenyls) propane, double (4- hydroxyl -3,5- diethyl phenyls) propane of 2,2-, double (the 4- hydroxyls-(3,5- hexichol of 2,2- Base) phenyl) propane, double (4- hydroxyl -3,5- dibromo phenyls) propane of 2,2-, 2,2- double (4- hydroxy phenyls) pentane, 2,4 '-dihydroxies Base-diphenyl methane, double (4- hydroxy phenyls) methane, double (4- hydroxyl -5- nitrobenzophenones) methane, 1,1- are double (4- hydroxy phenyls) Ethane, 3,3- double (4- hydroxy phenyls) pentane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double (4- hydroxy phenyls) sulfones, 2,4 '-two Hydroxy diphenyl sulfone, double (4- hydroxy phenyls) thioethers, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy -3,3 '-dichloro Base ether, 4,4 '-dihydroxy -2,5- diethoxy diphenyl ethers etc..

Oxirane (EO) the addition class ＞ of ＜ bisphenols

As oxirane (EO) addition class of bisphenols, such as it can enumerate and be carried out in the compound of foregoing bisphenols Material obtained from oxirane (EO) addition.

＜ fluorene compounds ＞

As fluorene compound, such as double (4- hydroxy phenyls) fluorenes of 9,9-, double (the 4- hydroxy-3-methyl benzene of 9,9- can be enumerated Base) fluorenes, double (4- hydroxyl -3- ethylphenyls) fluorenes of 9,9-, double (4- hydroxyl -3- n-propyls phenyl) fluorenes of 9,9-, double (the 4- hydroxyls of 9,9- Base -3- isopropyl phenyls) fluorenes, double (4- hydroxyl -3- n-butylphenyls) fluorenes of 9,9-, 9,9- be double (4- hydroxyl -3- secondary butyl phenenyls) Double (4- hydroxyl -3- cyclohexyl phenyls) fluorenes of double (the tertiary propyl group phenyl of the 4- hydroxyls -3-) fluorenes of fluorenes, 9,9-, 9,9-, 9,9- it is double (4- hydroxyls - 3- phenyls) fluorenes, double (4- (2- hydroxyl-oxethyls) phenyl) fluorenes of 9,9-, double (4- (2- the hydroxyl-oxethyls) -3- methylbenzenes of 9,9- Base) fluorenes, double (4- (2- the hydroxyl-oxethyls) -3- isopropyl phenyls) fluorenes of 9,9-, double (4- (2- the hydroxyl-oxethyls) -3- isobutyls of 9,9- Base phenyl) fluorenes, double (4- (2- the hydroxyl-oxethyls) -3- tert-butyl-phenyls) fluorenes of 9,9-, double (4- (2- the hydroxyl-oxethyls) -3- of 9,9- Cyclohexyl phenyl) fluorenes, double (4- (2- the hydroxyl-oxethyls) -3- phenyls) fluorenes of 9,9-, 9,9- it is double (4- (2- hydroxyl-oxethyls) - 3,5- 3,5-dimethylphenyls) fluorenes, double (4- (2- the hydroxyl-oxethyls) -3- tert-butyl group -6- aminomethyl phenyls) fluorenes of 9,9-, the double (4- (3- of 9,9- Hydroxyl -2,2- dimethyl propylenes epoxide) phenyl) fluorenes etc..

They can be used singly or in combination of two or more.But the material shown in except above-mentioned formula (1) Outside, the dihydroxy compounds with aromatic ring has the worry being had undesirable effect to optical characteristics, therefore, source in structure From the construction unit of such dihydroxy compounds relative to the structure list from the dihydroxy compounds in polycarbonate resin The total of member, it is preferably used below with 50 moles of %, more preferably with 20 moles of below %, further preferably with 5 moles of below % Use.Polycarbonate resin it is particularly preferred that without be derived from addition to the material shown in above-mentioned formula (1), have in structure The construction unit of the dihydroxy compounds of aromatic ring.

[containing ratio for being derived from the construction unit of dihydroxy compounds]

In the present invention, the contained structure list for being derived from the dihydroxy compounds shown in above-mentioned formula (1) in polycarbonate resin Member containing ratio relative to the construction unit from dihydroxy compounds total, preferably more than 20 weight %, more preferably For more than 25 weight %, more preferably more than 30 weight %.In addition, usually below 95 weight %, be preferably 90 weights Measure below %.

When the containing ratio of the construction unit is excessively lacked, heat resistance is small, there is the possibility of case hardness difference.In addition, the knot When the containing ratio of structure unit is excessively more, sometimes the glass transition temperature of polycarbonate resin excessively uprise and be difficult to be molded, Or water absorption rate deteriorates.

In addition, polycarbonate resin contains from selected from as the dihydroxy compounds shown in above-mentioned formula (4), above-mentioned formula (5) Dihydroxy compounds shown in shown dihydroxy compounds, above-mentioned formula (6), the dihydroxy compounds shown in above-mentioned formula (7) and The situation of the construction unit of the dihydroxy compounds of one or more of the group of dihydroxy compounds composition shown in above-mentioned formula (8) Under, its containing ratio relative to the construction unit from dihydroxy compounds contained in polycarbonate resin total, suitably , preferably 0.1 weight % less than 20 weight %, more preferably more than 0.1 weight % and below 18 weight %, enter One step is preferably more than 0.2 weight % and below 15 weight %.

By being included in polycarbonate resin dihydroxy is derived from shown in above-mentioned formula (4) to (8) more than above-mentioned lower limit The construction unit of based compound, so as to when the polycarbonate resin is melted and is molded, can prevent as caused by heat foreign matter, The generation of bubble, or prevent the coloring of polycarbonate resin.But the construction unit it is excessively more when, have when products formed is made resistance to The tendency that photosensitiveness reduces.

The whole dihydroxy compounds used in the manufacture of polycarbonate resin in the present invention can include reducing agent, resist The stabilizers such as oxidant, deoxidier, light stabilizer, antiacid, pH stabilizers or heat stabilizer.Specific dihydroxy in the present invention Compound is apt to deteriorate under acidity, it is therefore especially preferred that including alkaline stabiliser.

As alkaline stabiliser, such as long period type periodic table (Nomenclature of Inorganic can be enumerated Chemistry IUPAC Recommendations 2005) in 1 race or 2 races metal hydroxide, carbonate, phosphoric acid Salt, phosphite, hypophosphites, borate and soap, TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydrogen Amine-oxides, TBAH, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl hydroxide Ammonium, triethyl methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, tributyl benzyl hydroxide Ammonium, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphenyl ammonium hydroxide and The alkaline ammonium compounds such as butyl triphenyl ammonium hydroxide, diethylamine, dibutyl amine, triethylamine, morpholine, N-methylmorpholine, pyrrolidines, Piperidines, 3- amino -1- propyl alcohol, ethylenediamine, N methyldiethanol amine, diethyl ethylene diamine, 4-aminopyridine, PA, N, N- dimethyl -4-aminopyridine, 4- diethyl aminos yl pyridines, 2 hydroxy pyrimidine, 2- methoxypyridines, 4-methoxypyridine, The amine system chemical combination such as 2- dimethylaminos imidazoles, 2- methoxyl groups imidazoles, imidazoles, 2- mercaptoimidazoles, 2-methylimidazole and aminoquinoline Thing and two-(tert-butyl group) amine and 2,2,6,6- tetramethyl piperidines etc. is obstructed amine compound.In these stabilizers, from stabilization The effect of change is set out, preferably TMAH, imidazoles or the amine compound that is obstructed.

Content in whole dihydroxy compounds that these alkaline stabilisers use in the present invention is not particularly limited, this The foregoing specific dihydroxy compounds used in invention is unstable under acid state, it is preferred, therefore, that with comprising upper Stating the pH of the aqueous solution of the specific dihydroxy compounds of stabilizer turns into 7 or so mode, adds stabilizer.

When the amount of alkaline stabiliser is very few, it is possible to can not obtain preventing the effect that specific dihydroxy compounds is rotten, mistake When more, the modification of specific dihydroxy compounds is occasionally resulted in.Accordingly, with respect to each dihydroxy compounds used in the present invention, Alkaline stabiliser is preferably the weight % of the weight % of 0.0001 weight %~1, more preferably 0.001 weight %~0.1.

These alkaline stabilisers are contained in the dihydroxy compounds used in the present invention directly as polycarbonate resin Manufacture raw material in use, alkaline stabiliser turns into polymerization catalyst in itself, be not only difficult to control polymerization speed or quality but also Cause the deterioration of resin form and aspect.

Therefore, it is excellent for containing alkaline stabiliser in specific dihydroxy compounds or other foregoing dihydroxy compounds Choosing, in the manufacture raw material as polycarbonate resin before use, spent ion exchange resin or distillation etc. remove alkalescence stabilization Agent.

In addition, the specific dihydroxy compounds used in the present invention is easily slowly aoxidized due to oxygen, and therefore, keeping Or during operation during manufacture, in order to prevent the decomposition caused by oxygen, it is preferred that so that moisture is not mixed into, and using de- Oxygen agent or it is under nitrogen atmosphere.

(carbonic diester)

Polycarbonate resin in the present invention can be by include the dihydroxy of above-mentioned specific dihydroxy compounds Compound and carbonic diester obtain its polycondensation for raw material, using ester exchange reaction., generally can be with as the carbonic diester used Enumerate the carbonic diester shown in following formula (10).These carbonic diesters can be used alone, and can also mix two or more makes With.

In above-mentioned formula (10), A¹And A²The aliphatic alkyl of respectively substituted or unsubstituted carbon number 1~18 or substitution Or unsubstituted aromatic hydrocarbyl, A¹With A²It can be the same or different.A¹And A²Preferably substituted or unsubstituted aromatic series Alkyl, more preferably unsubstituted aromatic hydrocarbyl.

As the carbonic diester shown in above-mentioned formula (10), such as diphenyl carbonate (DPC) and carboxylol can be enumerated The substitution such as ester diphenyl carbonate, dimethyl carbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc..Wherein it is preferably dipheryl carbonate Ester or substitution diphenyl carbonate, particularly preferably diphenyl carbonate.

It should be noted that carbonic diester is sometimes comprising the impurity such as chloride ion, impurity hinder sometimes polymerisation or Deteriorate the form and aspect of gained polycarbonate resin, it is therefore preferable that being obtained using as desired by distillation etc. purify Carbonic diester.

＜ catalyst for ester exchange reaction ＞

Polycarbonate resin in the present invention be make above-mentioned dihydroxy compounds and carbonic diester carry out ester exchange reaction and Manufacture.More specifically, make its ester exchange, monohydroxy compound of by-product etc. is removed to outside system, so as to obtain.

During foregoing ester exchange reaction, polycondensation is carried out in the presence of catalyst for ester exchange reaction, the makrolon in the present invention The catalyst for ester exchange reaction (below, sometimes referred to simply as catalyst, polymerization catalyst) that can be used during resin manufacture may Very big influence is brought to the quality of polycarbonate resin obtained from reaction speed or polycondensation.

As the catalyst used, as long as meeting the transparency of the polycarbonate resin of manufacture, form and aspect, heat resistance, gasproof Time property and mechanical strength just do not limit.Such as can enumerate 1 race in long period type periodic table or 2 races (it is following, be simply denoted as " 1 race ", " 2 race ") metallic compound and alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and amine system chemical combination The alkali compounds such as thing.It is preferred that use 1 race's metallic compound and/or 2 race's metallic compounds.

As foregoing 1 race metallic compound, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide can be enumerated Caesium, sodium acid carbonate, saleratus, lithium bicarbonate, caesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, second Sour potassium, lithium acetate, cesium acetate, odium stearate, potassium stearate, lithium stearate, stearic acid caesium, sodium borohydride, potassium borohydride, boron hydrogen Change lithium, hydroboration caesium, phenylating boron sodium, phenylating boron potassium, phenylating boron lithium, phenylating boron caesium, sodium benzoate, Potassium Benzoate, Lithium benzoate, benzoic acid caesium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, the lithium of phosphoric acid hydrogen two, the caesium of phosphoric acid hydrogen two, disodium phenylphosphate, benzene Base dikalium phosphate, the lithium of phosphenylic acid two, the caesium of phosphenylic acid two, sodium, potassium, lithium, the alkoxide of caesium, phenates, the disodium salt of bisphenol-A, two Sylvite, dilithium salt and two cesium salts etc..Wherein from the viewpoint of the form and aspect of polymerization activity and gained polycarbonate resin, preferred lithium Compound.

As foregoing 2 race metallic compound, such as calcium hydroxide, barium hydroxide, magnesium hydroxide, hydroxide can be enumerated Strontium, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, second Sour barium, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and strontium stearate etc..

Wherein preferred magnesium compound, calcium compound or barium compound, from polymerization activity and the color of gained polycarbonate resin From the viewpoint of phase, further preferred magnesium compound and/or calcium compound, most preferably calcium compound.

It should be noted that can also auxiliarily group together with foregoing 1 race metallic compound and/or 2 race's metallic compounds Close and use the alkali compounds such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound, but it is especially excellent 1 race's metallic compound and/or 2 race's metallic compounds are used only in choosing.

As aforementioned base boron compound, for example, can enumerate tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, Trimethylethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethylbenzyl boron, triethyl group phenyl Boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyltriphenyl phosphonium boron, methyl triphenyl boron, butyl triphenyl boron Deng sodium salt, sylvite, lithium salts, calcium salt, barium salt, magnesium salts or strontium salt etc..

As aforementioned base phosphorus compound, such as triethyl phosphine, three n-propyl phosphines, tri isopropyl phosphine, three can be enumerated just Butyl phosphine, triphenylphosphine, tributylphosphine He quaternary alkylphosphonium salt etc..

As aforementioned base ammonium compounds, such as TMAH, tetraethyl ammonium hydroxide, tetrapropyl can be enumerated Ammonium hydroxide, TBAH, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl hydrogen-oxygen Change ammonium, triethyl methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, tributyl benzyl hydrogen-oxygen Change ammonium, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphenyl ammonium hydroxide With butyl triphenyl ammonium hydroxide etc..

As foregoing amine compound, such as 4-aminopyridine, PA, N, N- dimethyl -4- ammonia can be enumerated Yl pyridines, 4- diethyl aminos yl pyridines, 2 hydroxy pyrimidine, 2- methoxypyridines, 4-methoxypyridine, 2- dimethylamino miaows Azoles, 2- methoxyl groups imidazoles, imidazoles, 2- mercaptoimidazoles, 2-methylimidazole, aminoquinoline and guanidine etc..

For the dosage of above-mentioned polymerization catalyst, the whole dihydroxy compounds used in polymerization are per 1mol, and preferably 0.1 μm ol~300 μm ol, more preferably 0.5 μm of ol~100 μm ol, particularly preferably 1 μm of ol~50 μm ol.

Wherein use at least one kind of metal in the group and lithium formed comprising 2 races in by long period type periodic table In the case of compound, during especially with magnesium compound and/or calcium compound, as amount of metal, foregoing whole dihydroxies Compound is preferably set to 0.1 μm of more than ol, is more preferably set to 0.3 μm of more than ol, is particularly preferably set to 0.5 μm of more than ol per 1mol. And the upper limit is used as, preferably 20 μm of below ol, more preferably 10 μm of below ol, it is more preferably 5 μm of below ol, especially excellent Elect 3 μm of below ol as.

When catalytic amount is very few, polymerization speed is slack-off, therefore, it is desirable to the polycarbonate resin of desired molecular weight is obtained, must Polymerization temperature must correspondingly be improved.Therefore, the possibility that the form and aspect of gained polycarbonate resin deteriorate uprises, in addition, unreacted Raw material volatilized in polymerization midway, the molar ratio of dihydroxy compounds and carbonic diester is destroyed, and is not up to desired The possibility of molecular weight.On the other hand, when the dosage of polymerization catalyst is excessive, undesirable side reaction is concurrent, and having causes gained The possibility of the coloring of resin when the deterioration of the form and aspect of polycarbonate resin or processing and forming.

But when sodium, potassium or caesium largely include in polycarbonate resin in 1 race's metal, have and form and aspect are caused with bad shadow Loud possibility.Moreover, these metals are not only mixed into from used catalyst, also have from raw material or the mixed feelings of reaction unit Condition.Regardless of source, the total amount of the compound of these metals in polycarbonate resin is both preferably 1 weight with metal gauge Measure below ppm, more preferably below 0.5 weight ppm.

The manufacture method ＞ of ＜ polycarbonate resins

Polycarbonate resin in the present invention makes the dihydroxy for including specific dihydroxy compounds by using ester exchange reaction Based compound carries out polycondensation with carbonic diester and obtained.

Dihydroxy compounds as raw material preferably uniformly mixes with carbonic diester before ester exchange reaction.The temperature of mixing Usually more than 80 DEG C, preferably more than 90 DEG C.In addition, its upper limit is usually less than 250 DEG C, is preferably less than 200 DEG C, enters one Step is preferably less than 150 DEG C.Wherein it is suitably for more than 100 DEG C and less than 120 DEG C.

When the temperature of mixing is too low, there is the possibility that fusing speed is slow or melting degree is insufficient, it is bad to frequently result in solidification etc. Situation, when the temperature of mixing is too high, occasionally result in the heat deterioration of dihydroxy compounds, as a result, have to gained polycarbonate resin Form and aspect, the possibility that has undesirable effect of heat endurance.

The dihydroxy chemical combination for including specific dihydroxy compounds as the raw material of the polycarbonate resin in the present invention The operation that thing mixes with carbonic diester, preferably oxygen concentration be below 10vol%, more preferably 0.0001vol%~ 10vol%, more preferably 0.0001vol%~5vol%, it is particularly preferably under 0.0001vol%~1vol% atmosphere Carry out.By the way that for above range, the deterioration of form and aspect can be prevented.

In order to obtain the polycarbonate resin in the present invention, specific dihydroxy compounds is included relative to what is used in reaction Whole dihydroxy compounds, carbonic diester is preferably used with 0.94~1.04 molar ratio, more preferably 0.98~1.02, More preferably 1.00~1.01 molar ratio.The molar ratio becomes hour, the end benzene of the polycarbonate resin of manufacture Base is reduced, and easily produces bad order during shaping.

In addition, when the molar ratio becomes big, the speed reduction of ester exchange reaction sometimes or the poly- carbonic acid of desired molecular weight The manufacture of ester resin becomes difficult.The reduction of ester exchange reaction speed makes thermal history increase during polymerisation, as a result, having makes gained The possibility that form and aspect, the against weather of polycarbonate resin deteriorate.

And then relative to whole dihydroxy compounds comprising specific dihydroxy compounds, the molar ratio of carbonic diester During increase, the compound increase shown in the residual carbonic diester amount, above-mentioned formula (3) in gained polycarbonate resin, occasionally result in The problem of pollution, foul smell during shaping, bad order.

In the present invention, make dihydroxy compounds and the method for carbonic diester progress polycondensation in the presence of above-mentioned catalyst, be logical Often implemented using multiple reactors with the multistage.The form of reaction can be batch (-type), continous way or batch (-type) and continous way Combination in any means, it is preferred that it is also excellent continuous that polycarbonate resin, productivity ratio are obtained with less thermal history Formula.

Preferably, in polymerization initial stage, prepolymer is relatively obtained with low temperature, low vacuum, after polymerisation the phase, relatively with High temperature, high vacuum make molecular weight rise to defined value.In addition, the quality from control polymerization speed, gained polycarbonate resin From the viewpoint of, it is important that suitably select the pressure in the jacket temperature and Nei Wen, reaction system in each molecular weight stage.

For example, before polymerisation value as defined in reach, when any one of temperature, pressure change too quickly, unreacted Monomer distillate, upset the molar ratio of dihydroxy compounds and carbonic diester, cause the reduction of polymerization speed, or can not obtain To the polymer with defined molecular weight, end group, as a result, the possibility of the purpose of the present invention can not be reached by having.

And then in order to suppress the amount of monomer distillated, effectively, reflux condenser is used in polymer reactor, it is special Be not the polymerization initial stage more than unreacted monomer composition reactor in, the effect is big.The refrigerant imported in reflux condenser Temperature can suitably select according to used monomer, and generally, the temperature of the refrigerant imported in reflux condenser is in this time The porch of flow condenser is 45~180 DEG C, particularly preferably preferably 80~150 DEG C, 100~130 DEG C.

When the temperature of refrigerant is too high, capacity of returns is reduced, and its effect reduces.On the contrary, when the temperature of refrigerant is too low, have Originally the tendency that the distillation removal efficiency of the monohydroxy compound of removal reduces should be distilled.As refrigerant, using warm water, steam Air and heat Medium Oil etc., preferably steam, thermal medium oil.

In order to suitably maintain polymerization speed, suppress distillating and not destroying final polycarbonate resin for monomer Form and aspect, the species and the selected of amount of Above-mentioned catalytic agent are important.Polycarbonate resin in the present invention is preferably, using urging Agent, using multiple reactors, manufacture its polymerization with the multistage.

The reasons why being implemented and polymerize with multiple reactors is due to, at polymerisation initial stage, contained monomer is more in reaction solution, It is important, therefore, that polymerization speed needed for maintaining and suppress being vaporized for monomer, phase after polymerization, in order that balance to It polymerize side movement, the monohydroxy compound of by-product is fully distilled removal becomes important.In this way, the polymerisation bar that setting is different During part, from the viewpoint of production efficiency, it is preferred that use multiple polymer reactors of arranged in series.

As long as the reactor used in the manufacture of the polycarbonate resin in the present invention as described above for it is more than at least two i.e. Can.From viewpoints such as production efficiencys, preferably more than 3, more preferably 3~5, particularly preferably 4.In the present invention, Reactor, then can in the reactor, further with the different stage of reaction of multiple conditions, continuously if more than 2 Ground makes temperature, pressure change etc..

In the present invention, polymerization catalyst can also be added to raw material preparation vessel, raw material accumulator tank, or can also directly add Add to polymerization tank.Stability from supply, polymerization control from the viewpoint of, in supply to the raw material circuit midway before polymerization tank Catalyst supply lines are set, preferably supplied with the aqueous solution.

When the temperature of polymerisation is too low, productivity ratio is caused to reduce, the increase to the thermal history of product, when too high, not only Cause being vaporized for monomer, and have the decomposition for encouraging polycarbonate resin, the possibility of coloring.Specifically, the reaction of the 1st step In, be 130~210 DEG C as the temperature of the interior temperature of polymer reactor, be preferably 150~205 DEG C, more preferably 170~ 200℃。

In addition, the pressure (absolute pressure) as reaction system, in 1~110kPa, preferably 5~70kPa, further preferably Under 7~30kPa (absolute pressure) pressure, making the reaction time, side will produce for 0.1~10 hour, preferably 0.5~3 hour Monohydroxy compound distillation remove to outside reaction system and implement.

After 2nd step and the 2nd step, the pressure of the pressure of reaction system from the 1st step is slowly declined, then by caused by Monohydroxy compound is expelled to outside reaction system.Especially for the amount for controlling the compound shown in above-mentioned formula (3), the 2nd step with And the 2nd after step, be below 15kPa, finally, the pressure (absolute pressure) for making reaction system is below 600Pa, within temperature 190~240 DEG C of maximum temperature, preferably 195~235 DEG C, carry out usual 0.1~5 hour, preferably 0.1~4 hour, it is especially excellent Select 0.5~3 hour.

In order to obtain the polycarbonate resin of defined molecular weight, when excessively improving polymerization temperature, extending polymerization time, have The tendency that tone deteriorates.Coloring, heat deterioration, form and aspect especially for the polycarbonate resin that is inhibited be good and above-mentioned formula (3) the poor polycarbonate resin of the compound shown in, the maximum temperature of the interior temperature in the total overall reaction stage are preferably shorter than 240 DEG C, particularly preferably 210~235 DEG C.

In addition, the interior temperature in the total overall reaction stage is less than 3 hours for 210 DEG C less than reaction time at 240 DEG C When, the coloring of polycarbonate resin, heat deterioration can be suppressed, the good polycarbonate resin of form and aspect is obtained and then can control The yield of compound shown in above-mentioned formula (3), therefore it is preferred that, within particularly preferably 2.5 hours.

In addition, in order to suppress the reduction of the later half polymerization speed of polymerisation, be by the degradation inhibiting caused by thermal history Bottom line, it is preferred that in the terminal stage of polymerization, use piston fluidity and excellent, above-mentioned formula (3) institute of interface renewal property The compound shown controls excellent horizontal reactor.

From the viewpoint of utilization of resources, the monohydroxy compound of by-product is preferably, and is purified as needed Afterwards, the raw material as diphenyl carbonate, bisphenol-A etc. reuses.

Polycarbonate resin in the present invention as described above, after polycondensation, is generally allowed to cool solidification, with rotatably cutting Cutting mill etc. makes its pellet.The method of pellet does not limit, and can enumerate following method：From final polymer reactor to melt State is taken out, the method that solidification and pellet are allowed to cool in the form of strands；Will with molten condition from final polymer reactor Resin is supplied to single screw rod or double screw extruder, after melting extrusion, is allowed to cool the method for solidifying simultaneously pellet；Or, from most Final polymerization reaction device is taken out with molten condition, is allowed to cool solidification in the form of strands, after temporary transient pellet, is again supplied resin To single screw rod or double screw extruder, after melting extrusion, solidification simultaneously method of pellet etc. is allowed to cool.

In the case of using extruder, in extruder, decompression devolatilization or the addition that can also carry out residual monomer are usual The heat stabilizer known, nertralizer, ultra-violet absorber, light stabilizer, releasing agent, colouring agent, antistatic additive, lubrication prescription, lubricant, Plasticizer, compatibility agent, fire retardant etc. are so as to being kneaded.

Glass transition temperature, molecular weight of the melting mixing temperature-independent in polycarbonate resin in extruder, generally For 200~300 DEG C, preferably 210~280 DEG C, more preferably 220~270 DEG C.When melting mixing temperature is less than 200 DEG C, The melt viscosity of polycarbonate resin is high, becomes big to the load of extruder, productivity ratio reduces.Melting mixing temperature is higher than 300 DEG C When, the heat deterioration of polycarbonate resin becomes violent, causes the reduction of mechanical strength caused by the reduction of molecular weight, coloring, thin Gas when film is molded produces the generation of caused bubble.

The molecular weight of polycarbonate resin in the so obtained present invention can be represented with reduced viscosity.Reduced viscosity is led to Often it is more than 0.30dL/g, is preferably more than 0.35dL/g.In addition, the upper limit of reduced viscosity be usually below 1.20dL/g, it is excellent Elect below 1.00dL/g, more preferably below 0.80dL/g as.

When the reduced viscosity of polycarbonate resin is too low, there is the small possibility of the mechanical strength of products formed.It is in addition, more viscous than dense When spending big, mobility during shaping reduces, and has the tendency of to reduce productivity ratio, mouldability.It should be noted that makrolon The reduced viscosity of resin determines as follows：As solvent, using dichloromethane, by polycarbonate resin lipid concentration precision adjust to 0.6g/dL, with 20.0 DEG C ± 0.1 DEG C of temperature, it is measured using Ubbelohde viscosity tube.The detailed feelings of the assay method of reduced viscosity Condition is recorded in the item of embodiment.

[additive of polycarbonate resin]

＜ phosphorus series compounds ＞

In polycarbonate resin in the present invention, preferably comprise in order that polymerization catalyst is inactivated and then suppressed under high temperature Polycarbonate resin coloring and add, phosphorus series compound.

As the phosphorus series compound, preferably using be selected from by phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acids, phosphonate ester, It is at least one kind of in the group of acid phosphoric acid ester and aliphatic cyclic phosphite ester composition.What above-mentioned middle catalyst deactivation and coloring suppressed Effect it is more excellent be phosphorous acid, phosphonic acids, phosphonate ester, particularly preferably phosphonate ester.

As phosphonic acids, can enumerate phosphonic acids (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinyl phosphonate, decylphosphonic acid, Phenyl-phosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonate, 1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acids, 4- methoxybenzenes Base phosphonic acids, nitrilo- three (methylene phosphonic acid), propyl phosphonous acid acid anhydride etc..

As phosphonate ester, dimethyl phosphonate, diethyl phosphonate, phosphonic acids double (2- ethylhexyls) ester, phosphonic acids two can be enumerated Lauryl, the grease of phosphonic acids two, phosphonic acid diphenyl ester, phosphonic acids dibenzyl ester, dimethyl methyl phosphonate, diphenyl methylphosphonate, ethyl phosphine Diethyl phthalate, benzylphosphonic acid diethylester, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester, phenyl-phosphonic acid dipropyl, (methoxyl group Methyl) it is diethyl phosphonate, vinyl phosphonic diethyl phthalate, hydroxymethyl diethyl phosphonate, (2- hydroxyethyls) dimethyl phosphonate, right Methylbenzylphosphonic acid diethylester, diethylphosphonoacetic acid, diethylphosphonoacetic acid ethyl ester, the tertiary fourth of diethylphosphonoacetic acid Ester, (4- chlorobenzyls) diethyl phosphonate, diethyl phosphorocyanidate, cyano methyl diethyl phosphonate, 3,5- di-t-butyl -4- hydroxyls Benzylphosphonic acid diethylester, diethyl phosphonyl acetaldehyde diethyl acetal, (methylthiomethyl) diethyl phosphonate etc..

As acid phosphoric acid ester, can enumerate dimethyl phosphate, diethyl phosphate, di(2-ethylhexyl)phosphate vinyl acetate, phosphoric acid dipropyl, Double (butoxyethyl group) esters of dibutylphosphoric acid ester, phosphoric acid, phosphoric acid double (2- ethylhexyls) ester, the different tridecane ester of di(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphates The mixture of the di-phosphate esters such as grease, di(2-ethylhexyl)phosphate stearyl ester, diphenyl phosphate, phosphate dibenzyl ester or diester and monoesters, chlorine phosphoric acid The zinc salt etc. of diethylester, phosphoric acid stearyl ester.

Aliphatic cyclic phosphite ester is defined as being free of the phosphorous of aromatic group in the cyclic structure comprising phosphorus atoms Ester compound.Such as double (decyl) pentaerythritol diphosphites, double phosphorous of (tridecyl) pentaerythrite two can be enumerated Acid esters, distearyl pentaerythrityl diphosphite, double (2,6- tert-butyl-phenyls) pentaerythritol diphosphites, double (nonyls Phenyl) pentaerythritol diphosphites, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (bis- tertiary fourths of 2,6- Base -4- aminomethyl phenyls) pentaerythritol diphosphites, hydrogenated bisphenol A pentaerythritol phosphite polymer etc. be by dihydroxy Compound of polymer-type that compound is formed with pentaerythritol diphosphites etc..

They can be used alone, and can also mix two or more with ratio in any combination and use.

When the content of foregoing phosphorus series compound is very few, the effect that catalyst deactivation, coloring suppress is insufficient.In addition, foregoing phosphorus When the content of based compound is excessive, polycarbonate resin colours or produced on the contrary the coloring under wet heat condition.Therefore, phosphorus system The content of compound is not particularly limited, with the content meter of the phosphorus atoms in polycarbonate resin, be preferably set to 0.02 weight ppm with Upper and below 0.7 weight ppm, more preferably more than 0.05 weight ppm and below 0.65 weight ppm, particularly preferred 0.07 weight ppm Above and below 0.60 weight ppm.

Foregoing phosphorus series compound usually using phosphorus trichloride as initiation material, therefore, from unreacted reactant, departing from The chlorine-containing component of hydrochloric acid remains sometimes, but the amount of the chlorine atom contained in foregoing phosphorus series compound is preferably below 5 weight %.Chlorine When the residual quantity of atom is more, there is following worry：Corrode the metal portion of the manufacturing equipment of the foregoing phosphorus series compound of addition, or make to gather The heat endurance of carbonate resin reduces, and the molecular weight caused by promotion coloring, heat deterioration reduces.

Foregoing phosphorus series compound is it has been observed that preferably, using extruder, added to polycarbonate resin and be kneaded.It is special It is not, it is most useful that, polycarbonate resin is directly fed to extruder with molten condition after polymerisation, immediately into resin Add foregoing phosphorus series compound.And then so that the state of catalyst inactivation, is carried out at devolatilization from vaccum exhaust outlet in an extruder During reason, effectively devolatilization low molecular composition can be removed.

＜ hindered phenol compounds ＞

In polycarbonate resin in the present invention, also contain hindered phenol compound on the basis of foregoing phosphorus series compound, So as to expect that the tone of polycarbonate resin further improves.

As hindered phenol series compound, specifically, 2,6- DI-tert-butylphenol compounds, 2,4- di-tert-butyls can be enumerated Phenol, the 2- tert-butyl group -4- metoxyphenols, the 2- tert-butyl group -4,6- xylenols, 2,6 di tert butyl 4 methyl phenol, 2,6- Di-t-butyl -4- ethyl -phenols, DBH 2,5 di tert butylhydroquinone, n-octadecane base -3- (3 ', 5 '-di-t-butyls -4 '-hydroxy benzenes Base) propionic ester, the 2- tert-butyl groups -6- (3 '-tert-butyl group -5 '-methyl -2 '-hydroxybenzyl) -4- aminomethyl phenyls acrylate, 2,2 ' - Methylene-bis--(4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis--(6- cyclohexyl -4- methylphenols), 2,2 '-second Fork base-bis--(2,4- DI-tert-butylphenol compounds), four-[methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic ester] - Methane, n-octadecane base -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic ester, 1,3,5- trimethyls -2,4,6- three - (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, triethylene glycol-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic acid Ester], 1,6-HD-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], [3- (uncles of 3,5- bis- of pentaerythrite-four Butyl -4- hydroxy phenyls) propionic ester] etc..

They can be used alone, and can also mix two or more with ratio in any combination and use.

When polycarbonate resin is set into 100 parts by weight, the above-mentioned hindered phenol chemical combination of the polycarbonate resin in the present invention The parts by weight of the parts by weight of the content of thing preferably 0.001 parts by weight~1, more preferably 0.005 parts by weight~0.5, further preferred 0.01 The parts by weight of parts by weight~0.3.

It should be noted that for hindered phenol compound, following antioxidant, it is excellent also in the same manner as phosphorus series compound Choosing, using extruder, added to polycarbonate resin and is kneaded.

＜ antioxidants ＞

For oxidation resistant purpose, in the polycarbonate resin in the present invention, can also add commonly known anti-oxidant Agent.

As antioxidant, specifically, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous can be enumerated Sour three (2,4- di-tert-butyl-phenyls) esters, tridecyl phosphite, the monooctyl ester of phosphorous acid three, phosphorous acid three (octadecyl) ester, phosphorous Sour didecyl monophenyl, phosphorous acid dioctyl monophenyl, phosphorous acid diisopropyl monophenyl, phosphorous acid monobutyl diphenyl ester, Asia Mono phosphoric acid ester decyl diphenyl ester, phosphorous acid list octyl group diphenyl ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl-phenyls) octyl group phosphorous acid Ester, three (2,4- di-tert-butyl-phenyls) phosphite esters, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, Diphenyl phosphate list neighbour Biphenyl Ester, dibutylphosphoric acid ester, dioctylphosphoric acid ester, diisopropyl phosphate, 4,4 '-biphenylene di 2 ethylhexyl phosphonic acid four (2,4- di-tert-butyl-phenyls) ester, pentaerythrite four (3-thiopropionate), pentaerythrite four (3- lauryl thiopropionates), Glycerine -3- stearyl-thios propionic ester, N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxy-hydrocineamides), three (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid ester, 4,4 '-biphenylene di 2 ethylhexyl phosphonic acid four (2,4- di-tert-butyl-phenyls) Double { 1,1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls } -2,4,8 of ester, 3,9-, The oxaspiros of 10- tetra- (5,5) hendecane etc..

These antioxidants can be used singly or in combination of two or more.

When polycarbonate resin is set into 100 parts by weight, compounding amount preferably 0.0001 parts by weight of these antioxidants~ The parts by weight of the parts by weight of 0.1 parts by weight, more preferably 0.0005 parts by weight~0.08, further preferred 0.001 parts by weight~0.05.

＜ blueing agents ＞

In polycarbonate resin in the present invention, blueing agent can also be contained.

Fitted in blueing agent that the blueing agent used in the present invention can use from usual poly carbonate resin composition etc. Work as selection, its compounding amount can be adjusted and used, a variety of blueing agents can be used.

When polycarbonate resin (A) generally being set into 100 parts by weight, the content of the blueing agent in polycarbonate resin is preferred For 0.1 × 10^-4~10.0 × 10^-4Parts by weight, more preferably 0.3 × 10^-4~5.0 × 10^-4Parts by weight, particularly preferably 0.3 × 10^-4~2.0 × 10^-4Parts by weight.

The content of blueing agent is if 0.1 × 10^-4More than parts by weight, then easily make the polycarbonate resin plate in the present invention Promotion light fastness test before and after YI values for specific scope, make b* values be less than 3, therefore it is preferred that.On the other hand, blueing agent Content is if 10.0 × 10^-4Below parts by weight, then brightness will not reduce, and therefore, it is more than 90 easily to make L* values, therefore it is preferred that.

As the blueing agent used in the present invention, can be adapted to use the blueing used in poly carbonate resin composition Agent, from the viewpoint of absorbing wavelength, use maximum absorption wavelength preferably 520~600nm, more preferably 540~580nm dye Material.

As the concrete example of the preferable anthraquinone system blueing agent for the present invention, such as common name Solvent can be enumerated Violet13 [CA.No (Colour Index No) 60725；Trade (brand) name LANXESS Co. Ltd. systems " Macrolex Violet B ", three Water chestnut KCC system " Dia Resin Blue G ", Sumitomo Chemical Company Ltd's system " Sumiplast Violet B "], Solvent Violet14, common name Solvent Violet31 [CA.No68210；Trade (brand) name Mitsubishi chemical Co., Ltd System " Dia Resin Violet D "], Solvent Violet33 [CA.No60725；Trade (brand) name Mitsubishi chemical Co., Ltd system “Dia Resin Blue J”]、Solvent Violet36[CA.No68210；Trade (brand) name LANXESS Co. Ltd. systems “Macrolex Violet 3R”]、Solvent Blue45[CA.No61110；Trade (brand) name SAND CO., LTD. systems " Tetrazole Blue RLS "], common name Solvent Blue94 [CA.No61500；Trade (brand) name Mitsubishi chemical Co., Ltd System " Dia Resin Blue N "], common name Solvent Blue97 [LANXESS Co. Ltd. systems " Macrolex Blue RR "], common name Solvent Blue45, common name Solvent Blue87 and common name Disperse Violet28.

Wherein, preferred generic name Solvent Violet13 [LANXESS Co. Ltd. systems " Macrolex Violet B "], common name Solvent Violet36 [LANXESS Co. Ltd. systems " Macrolex Violet3R "], common name Solvent Blue97 [LANXESS Co. Ltd. systems " Macrolex Blue RR "], more preferably common name Solvent Violet13 [LANXESS Co. Ltd. systems " Macrolex Violet B "].

Wherein, dyestuff, the i.e. common name Solvent Violet13 of the structure shown in particularly preferred following formula (11) [CA.No (Colour Index No) 60725；Trade (brand) name LANXESS Co. Ltd. systems " Macrolex Violet B " and Mitsubishi Chemical Co. Ltd. system " Dia Resin Blue G ", Sumitomo Chemical Company Ltd's system " Sumiplast Violet B "].

In the present invention, additionally as blueing agent, maximum absorption wavelength preferably 520~600nm, more preferably can also be used 540~580nm pigment, above-mentioned dyestuff and pigment can also be applied in combination.

In the present invention, blueing agent can be used singly or in combination of two or more, preferably the dosage of blueing agent Few, the species of the blueing agent preferably used is also few.

In the present invention, the compounding period of the above-mentioned blueing agent of compounding, method of compounding be not special in polycarbonate resin (A) Limit.As compounding period, such as following method can be enumerated：Add together with raw material before polymerisation and directly gathered The method of conjunction；At the end of polymerisation, the method that is compounded in pipe arrangement, extruder；By polycarbonate resin and its He matches somebody with somebody method being compounded during mixture melting mixing etc..When carrying out melting mixing after polymerisation terminates and being compounded, make The regulation that is well dispersed, easily taking into account b* values and L* values of blue agent, therefore it is preferred that.It is direct with molten condition after polycondensation reaction terminates Thermal history, the mixed influence of oxygen can be suppressed to most by the method for be directed into extruder, being compounded blueing agent and carry out melting mixing Lower bound degree, therefore particularly preferably.

＜ ultra-violet absorbers ＞

The ultra-violet absorber used in the present invention is as long as there is specific physical property of the invention, absorption ultraviolet wavelength area The light in domain does not just limit.

The fusing point of the ultra-violet absorber used in the present invention is more than 135 DEG C.In addition, more preferably more than 140 DEG C, enter one Preferably more than 145 DEG C of step.

In addition, the fusing point of the ultra-violet absorber used in the present invention is less than 300 DEG C.In addition, more preferably less than 290 DEG C, Further preferred less than 280 DEG C.

By fusing point for should in the range of, roller pollution, the attachment on T die heads when can reduce extrusion film, film it is outer See and become good.Simultaneously, when the ultra-violet absorber is kneaded with extruder, the particle of ultra-violet absorber is completely molten Melt, it is dispersed, accordingly it is possible to prevent the film appearance of the particle from ultra-violet absorber is bad.

5% weightless temperature of the ultra-violet absorber used in the present invention is higher than 240 DEG C.Additionally, it is preferred that higher than 245 DEG C, More preferably higher than 250 DEG C.Ultra-violet absorber decomposes during by for that in the range of this, can prevent melting mixing.Thus, not only may be used To give full play to the ability of ultra-violet absorber, and it can prevent analyte from hindering continuous fortune in the exhaust outlet accumulation of extrusion Turn or analyte is accumulated in T die heads, roller etc. and destroys the outward appearance of film.

In the present invention, the ultra-violet absorber for having more than 0.45 parts by weight is contained relative to the parts by weight of polycarbonate resin 100. Additionally, it is preferred that containing more than 0.47 parts by weight, further preferably contain more than 0.5 parts by weight.

By in the range of this, object penetrating rate can be maintained in ultraviolet range, intended effect can be obtained.

In addition, containing relative to the parts by weight of polycarbonate resin 100 be 7 parts by weight below ultra-violet absorber.In addition, Further preferably below 5 parts by weight, further preferably below 3 parts by weight.By in the range of this, can not only to prevent roller The bad order of film caused by pollution, and can prevent the foreign matter caused by the aggregation of ultra-violet absorber from increasing.

It is concavo-convex to film transfer using the attachment as starting point when ultra-violet absorber is attached on roller, film can not be kept The uniformity of thickness, as a result, cause the uneven thickness of gained film, phase difference uneven.As the thickness and precision of film, preferably The thickness and precision of width is different and different according to the requirement physical property of each purposes, be usually within ± 10%, preferably ± Within 5%, within particularly preferably ± 3%.

In addition, when the fusing point of ultra-violet absorber is that above range is interior, addition is in above range, polycarbonate resin The glass transition temperature of composition will not decline to a great extent after ultra-violet absorber is added, and can maintain heat resistance.For group The glass transition temperature of compound, relative to the glass transition temperature for the polycarbonate resin for not adding ultra-violet absorber, Temperature difference is within 7 DEG C, is preferably within 5 DEG C, within more preferably 3 DEG C.

As preferable ultra-violet absorber, can enumerate triazine system, benzophenone series, enumerate BTA system, quinolinone system, Benzoic ether system, cyanoacrylate system, benzoxazole system etc..

(triazine system ultra-violet absorber)

As triazine system ultra-violet absorber, such as 2,4- diphenyl -6- (2- hydroxyl -4- methoxybenzenes can be enumerated Base) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- ethoxyl phenenyls) -1,3,5- triazines, 2,4- diphenyl-(2- hydroxyls Base -4- propoxyphenyls) -1,3,5- triazines, 2,4- diphenyl-(2- hydroxyl -4- butoxy phenyls) -1,3,5- triazines, 2,4- Diphenyl -6- (2- hydroxyl -4- butoxy phenyls) -1,3,5- triazines, 2,6- diphenyl -4- (2- hydroxyl -4- hexyl epoxide benzene Base) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- octyl groups phenyl) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- dodecyloxies phenyl) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- benzyloxyphenyls) -1, 3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- propoxyphenyls) -1,3,5- triazines, (2- hydroxyl -4- butyl phenyl ethers of 2,4,6- tri- Base) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- butoxy phenyls) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyls -4- oneself Base phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- octyl groups phenyl) -1,3,5- triazines, (the 2- of 2,4,6- tri- Hydroxyl -4- dodecyloxies phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- benzyloxyphenyls) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- ethoxy ethoxies phenyl) -1,3,5- triazines, (2- hydroxyl -4- Butoxyethoxies of 2,4,6- tri- Phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyl -4- propoxyl group ethoxyl phenenyl) -1,3,5- triazines, (the 2- hydroxyls of 2,4,6- tri- Base -4- methoxycarbonylpropyls phenyl) -1,3,5- triazines, (2- hydroxyl -4- ethoxycarbonylethyl group the epoxides of 2,4,6- tri- Phenyl) -1,3,5- triazines, (2- hydroxyls-the 4- (1- (2- ethoxyhexyls epoxide) -1- oxopropan -2- bases epoxide) of 2,4,6- tri- Phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- ethoxyl phenenyls) -1,3,5- triazines, (the 2- of 2,4,6- tri- Hydroxy-3-methyl -4- propoxyphenyls) -1,3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- butoxy phenyls) -1, 3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- butoxy phenyls) -1,3,5- triazines, (2- hydroxyl -3- first of 2,4,6- tri- Base -4- hexyls phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- octyl groups phenyl) -1,3,5- three Piperazine, 2,4,6- tri- (2- hydroxy-3-methyl -4- dodecyloxies phenyl) -1,3,5- triazines, (2- hydroxyl -3- first of 2,4,6- tri- Base -4- benzyloxyphenyls) -1,3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- ethoxy ethoxies phenyl) -1,3, 5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- butoxyethoxies base) -1,3,5- triazines, 2,4,6- tri- (2- hydroxyls - 3- methyl -4- propoxyl group ethoxyl phenenyl) -1,3,5- triazines, (2- hydroxy-3-methyl -4- the methoxycarbonylpropyls of 2,4,6- tri- Phenyl) -1,3,5- triazines, 2,4,6- tri- (2- hydroxy-3-methyl -4- ethoxycarbonylethyl groups phenyl) -1,3,5- Triazine, (2- hydroxy-3-methyls -4- (1- (2- ethoxyhexyls the epoxide) -1- oxopropan -2- bases epoxide) benzene of 2,4,6- tri- Base) -1,3,5- triazines, double (2,4- 3,5-dimethylphenyls) -6- (2- hydroxyl -4-N- octyl groups the phenyl) -1,3,5- triazines of 2,4-, 2- (4,6- diphenyl -1,3,5- triazine -2- bases) -5- (2- (2- ethyl hexanoyls epoxide) ethyoxyl) phenol etc..

Wherein, as commercially available product, double (2, the 4- 3,5-dimethylphenyl) -6- (2- hydroxyl -4-N- octyl group epoxides of 2,4- can be enumerated Phenyl) -1,3,5- triazines (CHEMIPRO KASEI KAISHA, LTD. systems " Kemisorb102 "), 2,4,6- tri- (2- hydroxyls - 3- methyl -4- hexyls phenyl) -1,3,5- triazines (Asahi Denka Co., Ltd.'s system " ADK STAB LA-F70 "), 2- (4,6- bis- Phenyl -1,3,5- triazine -2- bases) -5- (2- (2- ethyl hexanoyls epoxide) ethyoxyl) phenol (Asahi Denka Co., Ltd. system " ADK STAB LA-46 "), 2,4- diphenyl -6- (2- hydroxyl -4- hexyls phenyl) -1,3,5- triazines (BASF Japan strain formula meetings Society " Tinuvin 1577 ").

(benzophenone series ultra-violet absorber)

As benzophenone series ultra-violet absorber, such as 2,4-DihydroxyBenzophenone, 2- hydroxyl -4- first can be enumerated Epoxide benzophenone, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- behzyloxybenzophenones, 2- hydroxyl -4- methoxyl groups Benzophenone -5- sulfonic acid, BP-4 trihydrate, 2- hydroxyl -4- dodecyloxies-two Benzophenone, 2- hydroxyls -4- octadecane epoxides-benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones, 2,2 ', 4,4 '-four Dihydroxy benaophenonel, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulphurs Sour sodium benzophenone, double (5- benzoyl -4- hydroxyl -2- methoxyphenyls) methane, 2- hydroxyl -4- dodecyls epoxide two Benzophenone, 2- hydroxyl -4- methoxyl groups -2 '-carboxyl benzophenone, 4,4 '-bis- (diethylamino) benzophenone etc..

Wherein, as commercially available product, can enumerate BP-2 (Shipro Kasei Kaisha, Ltd. system " SEESORB 106 ", BASF Japan Co., Ltd. " Uvinul3050 "), 2,2 '-dihydroxy -4,4 '-dimethoxy Benzophenone (Shipro Kasei Kaisha, Ltd. system " SEESORB 107 ", BASF Japan Co. Ltd. systems “Uvinul3049”)。

(enumerate BTA system ultra-violet absorber)

As enumerate BTA system ultra-violet absorber, such as 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) benzo three can be enumerated Azoles, 2- [2 '-hydroxyl -3 ', 2- (2 '-hydroxyl-the 3 '-tert-butyl group -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyls -5 '-methyl Phenyl) BTA, 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl]-BTA, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl - Phenyl)-BTA, 2- (2 '-hydroxyl-the 3 '-tert-butyl group -5 '-aminomethyl phenyl) -5- chlorobenzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl-phenyl) -5- chlorobenzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-two tertiary pentyls)-BTA, 2- (2 '-hydroxyls Base -3 ', 5 '-di-tert-pentyl-phenyl) -5- chlorobenzotriazoles, 2- (2 '-hydroxyls -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydrochysene phthalyl Formimino group) -5 '-aminomethyl phenyl) BTA, 2- (2- hydroxyl -3,5- di-tert-pentyl-phenyls), 2- (2 '-hydroxyls -5 '-tertiary pungent Base phenyl) BTA, 2,2 '-di-2-ethylhexylphosphine oxide [4- (1,1,3,3- tetramethyl butyls) -6- (2H- BTA -2- bases) benzene Phenol] etc..

Wherein, as commercially available product, 2 can be enumerated, 2 '-di-2-ethylhexylphosphine oxide [4- (1,1,3,3- tetramethyl butyl) -6- (2H- benzene And triazole -2- bases) phenol] (Asahi Denka Co., Ltd.'s system " ADK STAB LA-31 ", CHEMIPRO KASEI KAISHA, LTD. Make " Kemisorb279 "), 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTA (Shipro Kasei Kaisha, Ltd. systems “SEESORB 709”)。

(indoles system ultra-violet absorber)

As indoles system ultra-violet absorber, the compound shown in following formula (12) can be used, such as 2- can be enumerated [(1- methyl -2- phenyl -1H- indol-3-yls) methylene] propane dintrile (Orient Chemical Industries Co., Ltd. make " BONASORB UA-3901 ") etc..

In above-mentioned formula (12), R₁~R₃Represent arbitrary substituent.Wherein, R₂And R₃One or more can be substituted, substituted During many places, each substituent can be with identical or different.

(quinolinone system ultra-violet absorber)

As quinolinone system ultra-violet absorber, the compound shown in following formula (13) can be used, such as can enumerate 4- hydroxyls -3- [(phenyl imine base) methyl] -2 (1H)-quinolinones (Orient Chemical Industries Co., Ltd. System " BONASORB UA-3701 ") etc..

In above-mentioned formula (13), R₄~R₆Represent arbitrary substituent.Wherein, R₅And R₆One or more can be substituted, substituted During many places, each substituent can be with identical or different.

(benzoic ether system ultra-violet absorber)

As benzoic ether system ultra-violet absorber, such as 2,4- di-tert-butyl-phenyls -3 ' can be enumerated, 5 '-two tertiary fourths Base -4 '-hydroxybenzoate, 2,6- di-tert-butyl-phenyls -3 ', 5 '-di-t-butyl -4 '-hydroxybenzoate, hexadecane Base -3,5- di-tert-butyl-4-hydroxybenzoic acids ester, n-octadecane base -3,5- di-tert-butyl-4-hydroxybenzoic acid esters etc..These Benzoic ether system ultra-violet absorber can use as ultra-violet absorber.

(cyanoacrylate system ultra-violet absorber)

As cyanoacrylate system ultra-violet absorber, such as 2 '-ethylhexyl -2- cyano group -3,3- bis- can be enumerated Phenyl acrylate, ethyl -2- cyano group -3- (3 ', 4 '-methylenedioxyphenyl base)-acrylate etc..These alpha-cyanoacrylates Ester system ultra-violet absorber can use as ultra-violet absorber.

In the present invention, ultra-violet absorber can be used alone, two or more can also be applied in combination.

Wherein, from the few aspect of heat endurance, the coloring to resin, preferably triazine system, enumerate BTA system, quinolinone System, indoles system.

(other ultra-violet absorbers)

In addition to above-mentioned ultra-violet absorber, as other ultra-violet absorbers, fluorescent whitening agent can also be used.Such as 7- (dimethylamino) -4- methylcoumarins, the double (the 5- tert-butyl group -2- benzoxazoles of 2,5- for benzoxazole system can be enumerated Base) thiophene (BASF Japan Co., Ltd. " TINOPAL OB "), 4,4 '-bis- (2- benzoxazolyls) Stilbene etc..Wherein, preferred benzene Bing oxazole systems.

[poly carbonate resin composition]

Poly carbonate resin composition in the present invention for example can also be with aromatic polycarbonate resin, fragrant adoption The synthetic resin such as ester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic acid, amorphous polyolefin, ABS, AS, gather The one kind or two or more mixings such as Biodegradable resin, the rubber such as lactic acid, poly- butanedioic acid styrene esters, with the shape of polymer alloy Formula uses.

And then the polycarbonate resin used in the present invention can add resin group together with these other resin components Usually used nucleator, fire retardant, flame retardant, inorganic filler, modified impact agent, hydrolysis inhibitor, foaming in compound Agent, dye pigment etc. form poly carbonate resin composition.

[manufacture method of polycarbonate resin extrusion molding article]

＜ manufacture methods ＞

The polycarbonate resin film of the present invention is by containing the polycarbonate resin used in the present invention according to conventional method Film obtained from the resin combination shaping of fat, ultra-violet absorber and other additives as needed.The makrolon The autofrettage of resin film is preferably the melting extrusion methods of forming such as the T die heads method of forming, film blowing, particularly preferably T die heads The method of forming.

The polycarbonate resin film of the present invention is located at before image display device or during the back side, the image of display due to Defect, distortion etc. it is impaired and can not be visual.Therefore, by the melting extrusion method of forming carry out filming when, it is desirable to gel, bubble, The foreign matter bad point that yellowing etc. is derived from resin is few, and is uniform thickness on width, without optics such as local phase differences Distortion.

Resin temperature when melting extrusion is molded is usually 150~265 DEG C, is preferably 200 DEG C~260 DEG C, particularly preferably For 210 DEG C~250 DEG C of scope.During less than aforementioned temperature, it is too high and extrude load and uprise there is melt viscosity.The opposing party Face, during higher than aforementioned temperature, at least polycarbonate resin in resin combination starts to thermally decompose, and produces coloring, viscosity reduces Deng degradation phenomena.

On the basis of control resin temperature becomes the melt viscosity suitable for shaping, make the discharge of raw material feeding machine The mutual feedback controls such as amount, the liquor charging amount of the screw speed of extruder, gear pump, make resin extruded rectification, so as to carry The thickness and precision of high film.The thickness and precision of preferable width according to the different and different of the requirement physical property of each purposes, Usually within ± 10%, it is preferably within ± 5%, within particularly preferably ± 3%.

In the case of the continuous thickness measurement machine of traversing type in the circuit being continuously film-made being present in the thickness measurement of width, Evaluated in measure each point.When carrying out the on-line determination in cut film, thick with amesdial with width 50mm intervals The point of the measure such as degree meter is evaluated.Herein, the both ends of the film of extrusion are thickening due to contracting etc., and therefore, it is exclusion point Cut and the evaluation in the range of the width of discarded part.

Chill-roll temperature is preferably set to Tg-100 relative to the glass transition temperature (Tg) of poly carbonate resin composition DEG C~Tg+50 DEG C, more preferably Tg-80 DEG C~Tg+40 DEG C, particularly preferably Tg-60 DEG C~Tg+30 DEG C.More specifically, it is cold But roll temperature is preferably 20~170 DEG C, more preferably 40~160 DEG C, particularly preferably 60~150 DEG C.

When chill-roll temperature is less than aforementioned temperature, gear line, or local optical distortion inequality are produced on film surface Become apparent.When on the other hand, higher than aforementioned temperature, the film for having extrusion is difficult to be peeling mark from chill roll stripping, or The contaminated tendency of roller.

In addition, the polycarbonate resin film in the present invention can be oriented film, can be stretched along at least one direction And form phase-contrast film.

For the method for its stretching, it can be used alone, simultaneously or sequentially can also be stretched using free end, fixing end is drawn Stretch, free end shrink, fixing end shrink etc. various drawing process.In addition, on draw direction, can also be hung down with horizontal direction Nogata is carried out to the various directions such as thickness direction, diagonally opposed, dimension, is not particularly limited.It is preferred that horizontal single shaft can be enumerated Drawing process, in length and breadth simultaneously biaxial drawing method, in length and breadth successively biaxial drawing method etc..

As the means of stretching, any appropriate stretching-machine such as tentering stretching-machine, biaxial stretcher can be used.

Draft temperature can suitably select appropriate value according to purpose.Stretching is preferably, relative to reel film The glass transition temperature of (that is, as the makrolon in the present invention of the material of preparing of reel film or its resin combination) (Tg), carried out with Tg-20 DEG C~Tg+30 DEG C, preferably Tg-10 DEG C~Tg+20 DEG C, more preferably Tg-5 DEG C~Tg+10 DEG C of scope. By condition as selection, phase difference value easily becomes uniform, and film is not easy to become gonorrhoea.Specifically, above-mentioned draft temperature For 90 DEG C~210 DEG C, more preferably 100 DEG C~200 DEG C, particularly preferably 100 DEG C~180 DEG C.

Stretching ratio can suitably be selected according to purpose, and non-stretched situation is set into 1 times, preferably more than 1.1 times And less than 6 times, more preferably more than 1.5 times and less than 4 times, be more preferably more than 1.8 times and less than 3 times, particularly preferred For more than 2 times and less than 2.5 times.

When stretching ratio is excessively big, fracture during stretching, and the long-term use under hot conditions are not only likely to result in The variation inhibition of caused optical characteristics is possible to diminish, when excessively low, under desired thickness, it is possible to Wu Fafu Give desired optical characteristics.

Draw speed can also suitably select according to purpose, with the distortion speedometer shown in following formula, be usually 50% ~2000%, it is preferably 100%~1500%, more preferably 200%~1000%, particularly preferably 250%~500%.Draw Stretch speed it is excessively big when, it is possible to cause stretching when fracture or hot conditions under long-term use caused by optical characteristics Variation become big.In addition, draw speed excessive hour, not only productivity ratio reduction, and in order to obtain desired phase difference, it is necessary to Excessively increase stretching ratio.

The speed that distorts (%/minute)={ length (mm) of draw speed (mm/ minutes)/reel film } × 100

Furthermore it is possible to carry out heat fixation processing in heating furnace after the stretch, the width of stenter can also be controlled or adjusted Whole roller peripheral speed carries out the process that relaxes.

By carrying out the processing, the variation of optical characteristics caused by the long-term use under hot conditions can be suppressed.

The film of the present invention is by suitably selecting to adjust the treatment conditions in such stretching process so as to making.

The upper limit of the thickness of the film of the present invention is less than 120 μm.More preferably less than 50 μm, more preferably 30 μm Below.The upper limit by the thickness of film is in the range of being somebody's turn to do, to manufacture film of the same area with less material of preparing can Formed, therefore be effective.And then will can be maintained using the thinner thickness of the product of the film, and can control uniformly Property, to requiring that the equipment of the slim homogenieity of accuracy is useful.

On the other hand, the lower limit of the thickness of film of the invention is more than 5 μm.Preferably more than 10 μm.The thickness of film When excessively thin, film operation becomes extremely difficult, and fold is produced in manufacture, or is difficult to sometimes and other films, the piece such as protective film Deng stickup.Lower limit by the thickness of the film of the present invention is in the range of being somebody's turn to do, can solve the problems, such as such.

The present invention film can be used as polarisation part protective film, it is possible to implement hard conating, with antireflection process, prevent Processing for the purpose of tacky, diffusion or even anti-glare, before being bonded, as surface treatment, can also implement corona discharge Processing, ultraviolet treatment with irradiation etc..

The lower limit of the wavelength 380nm of the film of present invention light transmittance is more than 0.001%.It is preferred that more than 0.005%, more It is preferred that more than 0.008%, further preferred more than 0.01%.When transmissivity is too low, the content of ultra-violet absorber necessarily becomes more, There is the possibility of the bad order for producing film etc..

In addition, the upper limit of the wavelength 380nm of the film of present invention light transmittance is less than 15%.It is preferred that less than 8%, it is more excellent Select less than 1%, further preferred less than 0.1%.When transmissivity is too high, for polarisation part protective film in the case of, have polarisation The worry that part is deteriorated due to ultraviolet.

By the use of the present invention film as phase-contrast film when, preferred more than the 100nm of phase difference in the face at 548nm, more It is preferred that more than 110nm, further preferred more than 120nm.

Additionally, it is preferred that below 200nm, more preferably below 180nm, further preferred below 160nm.Pass through phase difference in face For in the range of this, the quality using obtained Polarizer of the invention, the image of image display device is extremely distinct, becomes good.Tool For body, when polarized sunglasses observation is using obtained Polarizer of the invention, image display device, due to visual angle Change and caused rainbow pattern etc. is not likely to produce.

The foreign matter ＞ of ＜ films

The foreign matter of film not only breaks up the quality of film, and from the viewpoint of the productivity ratio of film and unexcellent Choosing.It is as described above, particularly effective to be in order to reduce the foreign matter of film, reduce the specific chemical combination in resin combination The content of thing, the generation for preventing non-liquefactent during melting mixing, the hair of the film roller pollution oozed out when being film-made from film It is raw.

For the foreign matter in film, evaluated with method described later, preferably 15/m²Below, more preferably 10/m²With Under, further preferred 5/m²Below, particularly preferred 3/m²Below.During in the presence of foreign matter more than the numerical value, film is not only broken up Outward appearance, and the optics physical property of film is had a significant effect.

Embodiment

Hereinafter, according to embodiment to the present invention be further described in detail, as long as but the present invention be no more than its purport just Do not limited by following examples.

[evaluation method]

In below, the evaluation of the physical property and characteristic of polycarbonate resin is carried out by the following method.

(1) measure of reduced viscosity

The sample of polycarbonate resin is dissolved in dichloromethane, prepare concentration 0.6g/dL polycarbonate resin solution. Using Sen You physics and chemistry Industrial Co., Ltd Ubbelohde type viscosity tube, it is measured at 20.0 DEG C ± 0.1 DEG C of temperature, according to solvent Passage time t₀With the passage time t of solution, relative viscosity η is obtained by following formula (i)_rel, according to relative viscosity η_rel, pass through Following formula (ii) obtains specific viscosity η_sp。

η_rel=t/t₀···(i)

η_sp=(η-η₀)/η₀=η_rel-1···(ii)

By specific viscosity η_spDivided by concentration c (g/dL), obtain reduced viscosity η_sp/c.The value is higher, and molecular weight is bigger.Than dense The value of viscosity is bigger, can obtain the more excellent film of mechanical strength.

(2) 380nm ultraviolet transmittance

Light transmittance at wavelength 380nm according to JISK0115 (2004) (photometric analysis of extinction general rule), using it is ultraviolet can Determined depending on spectrophotometer (Hitachi High-Technologies Corporation U2900).

(3) 5% weightless temperatures

Using TG-DTA6300 (Seiko systems), under a nitrogen (flow 200ml/ minutes), while by sample about 10mg from room temperature 500 DEG C of sides are warming up to 10 DEG C/min to be measured, and obtain 5% weightless temperature.

(4) fusing point

It is measured using differential scanning calorimetry (DSC) (SII NanoTechnology Inc. DSC6220).By sample about 10mg is put into the aluminium dish of same company system and sealed, under the stream of nitrogen gas of 50mL/ minutes, with 10 DEG C/min of programming rate From room temperature to 400 DEG C, the temperature on the summit of melting peak is obtained.

(5) glass transition temperature (Tg) of polycarbonate resin

The glass transition temperature of polycarbonate resin uses differential scanning calorimetry (DSC) (SII NanoTechnology Inc. DSC6220 processed) determine.Polycarbonate resin sample about 10mg is put into the aluminium dish of same company system and sealed, From room temperature to 250 DEG C under the stream of nitrogen gas of 50mL/ minutes, with 20 DEG C/min of programming rate.After keeping temperature 3 minutes, with 20 DEG C/min of speed is cooled to 0 DEG C.Kept for 3 minutes at 0 DEG C, be warming up to 200 DEG C again with 20 DEG C/min of speed.Root According to the DSC data obtained in the 2nd heating, using extrapolation glass transition start temperature.

(6) phenol and the measure of the content of the compound shown in formula (3)

Precision weighing polycarbonate resin sample about 1g, is dissolved in dichloromethane 5mL and solution is made, then turned into total amount 25mL mode adds acetone, carries out reprecipitation processing.Then, the treatment fluid is filtered with 0.2 μm of disc filter, utilizes liquid Phase chromatography is quantified.

(7) film forming and roller pollution evaluation

With 2kg/ hours, Co., Ltd. O CS gel counter FSA thin film inspections circuit (barrels set temperature is used： 240 DEG C, T die heads (width 150mm, design temperature：240 DEG C), chill roll (design temperature：105 DEG C)), it is shaped to each thickness Film, according to following benchmark, carry out the judgement of the presence or absence of roller pollution generation.

0 minute less than in 15 minutes be visually able to confirm that roller pollution situation：××

15 minutes less than in 30 minutes be visually able to confirm that roller pollution situation：×

30 minutes less than in 60 minutes be visually able to confirm that roller pollution situation：△-

60 minutes less than in 90 minutes be visually able to confirm that roller pollution situation：△

90 minutes less than in 120 minutes be visually able to confirm that roller pollution situation：○-

120 minutes less than in 150 minutes be visually able to confirm that roller pollution situation：○

150 minutes less than in 180 minutes be visually able to confirm that roller pollution situation：◎

(8) thickness and thickness and precision of film

Since gained film, in about 10m parts, from the center of film, for two width 30mm scope, with TD Direction 10mm intervals, use contact thickness gauge (Ono Sokki Co Ltd's product name " Digital Linear Gauge DG- 933 ") thickness of film, is determined.Herein, so-called " thickness of film " refers in the present invention, calculates the total flat of foregoing measured value .In addition, the numerical value obtained by following formula is used as it is so-called " thickness and precision " in the present invention.

Thickness and precision (%)={ (maximum deviation for deviateing the thickness of film)/(thickness of film) } × 100

Wherein, in formula (" maximum deviation for deviateing the thickness of film " refers to, above-mentioned each measured value and average value be (film Thickness) difference in maximum.)

The numerical value of thickness and precision is smaller, is more shown to be the film with thickness evenly.

(9) film foreign matter

Sample for being cut into width 50mm, length 200mm from gained film, visually to count the diameter in the sample The presence number for the foreign matter that more than 150 μm of (being major diameter in the case of elliptoid).The presence number of foreign matter is fewer, such as optically thin Film excellent during film.

[using raw material]

The abbreviation of the compound used in following embodiment and comparative example and manufacturer are as described below.

＜ dihydroxy compounds ＞

·ISB：Isobide [ロ ケ ッ ト フ ル ー レ company systems]

·CHDM：1,4 cyclohexane dimethanol [SKChemical Co. Ltd. systems]

·TCDDM：Tricyclodecane Dimethanol [OXEA Co. Ltd. systems]

＜ carbonic diesters ＞

·DPC：Diphenyl carbonate [Mitsubishi chemical Co., Ltd's system]

＜ hindered phenol compounds ＞

·Irganox1010：Pentaerythrite-four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester] [BASF Japan Co. Ltd. systems]

＜ phosphorus series compounds ＞

Phosphorous acid [peaceful Chemical Industries Co. Ltd. system] (molecular weight 82.0)

·AS2112：Three (2,4- di-tert-butyl-phenyls) phosphite esters [Asahi Denka Co., Ltd.'s system] (molecular weight 646.9)

＜ ultra-violet absorbers ＞

·UVA-1：LA-31 [Asahi Denka Co., Ltd.'s system]

·UVA-2：LA-36 [Asahi Denka Co., Ltd.'s system]

·UVA-3：LA-F70 [Asahi Denka Co., Ltd.'s system]

·UVA-4：BONASORB UA-3701 [Orient Chemical Industries Co., Ltd. system]

·UVA-5：Uvinul3049 [BASF Japan Co. Ltd. systems]

·UVA-6：Uvinul3050 [BASF Japan Co. Ltd. systems]

·UVA-7：Seesorb709 [Shipro Kasei Kaisha, Ltd. system]

·UVA-8：Tinuvin234 [BASF Japan Co. Ltd. systems]

·UVA-9：TINOPAL OB [BASF Japan Co. Ltd. systems]

·UVA-10：Cyasorb UV-5411 [Japanese Cytec Industries Inc. systems]

Physical property possessed by ultra-violet absorber is concluded and is shown in table 1 below.

[table 1]

The manufacture method of polycarbonate resin

[Production Example 1]

Using by the device of vertical mixing reactor 3 and the device of Horizontal stirring reactor 1 and twin-screw extrusion mechanism into it is continuous Polymerization unit, carry out the polymerization of polycarbonate resin.ISB and CHDM and DPC is set to be melted respectively in tank, with mol ratio ISB/ CHDM/DPC=0.700/0.300/1.010 is continuously fed to the 1st vertical mixing reactor.Simultaneously, catalyst will be used as The aqueous solution of calcium acetate monohydrate supplied in a manner of turning into 1.5 μm of ol relative to whole dihydroxy compounds 1mol to the 1 vertical mixing reactor.In a manner of the mean residence time in the 1st vertical mixing reactor turns into 90 minutes, control is located at The aperture of the valve of the transfer pipe arrangement of reactor bottom, and liquid level is remained necessarily.Discharge anti-autoreactor bottom Liquid is answered then to be continuously fed into the 2nd vertical mixing reactor, the 3rd vertical mixing reactor, the 4th Horizontal stirring reactor successively [Hitachi Plant Technologies, Ltd. twin-screws Bipitch bucket].1st vertical mixing reactor and the 2nd vertical Stirred reactor possesses reflux condenser, by adjusting reflux ratio, suppresses distillating for unreacted dihydroxy compounds and DPC.

The reaction temperature of each reactor, internal pressure, holdup time are set to：1st vertical mixing reactor：190℃、 25kPa, 90 minutes, the 2nd vertical mixing reactor：195 DEG C, 10kPa, 45 minutes, the 3rd vertical mixing reactor：210℃、 3kPa, 45 minutes, the 4th Horizontal stirring reactor：230 DEG C, 0.5kPa, 90 minutes.It is dense viscous with the ratio of gained polycarbonate resin Degree operates as 0.61dL/g to 0.64dL/g mode when the internal pressure to the 4th Horizontal stirring reactor is finely adjusted.

Polycarbonate resin is continuously taken out from the 4th Horizontal stirring reactor, then directly supplies resin with molten condition To double screw extruder [Corporation Japan Steel Works TEX30 α].Extruder has 3 vaccum exhaust outlets, by resin The devolatilization of residual low molecular composition remove.The masterbatch pellet of phosphorous acid is coated with from the nearby supply of the 1st exhaust outlet, relative to poly- Carbonate resin addition phosphorous acid 0.65ppm (0.2ppm is calculated as with the amount of phosphorus atoms), for tree in the 2nd exhaust outlet nearby Fat add the weight ppm of water 2000, carry out water filling devolatilization, from the 3rd exhaust outlet nearby supply AS2112 500ppm, Irganox10101000ppm.By barrel temperatures set it is 220 DEG C, screw speed sets in extruder (all 10 machine barrels) For 230rpm.Resin temperature at outlet of extruder is 262 DEG C.

Pass through the polycarbonate resin of extruder then with molten condition directly by filter, after foreign body filtering, With strand form from mould discharge, water cooling, and make its solidify after, utilize rotary cutting machine carry out pellet.The vitrifying of pellet Transition temperature is 122 DEG C.Using gained polycarbonate resin as PC1.

[Production Example 2]

Continuously supplied with mol ratio ISB/CHDM/DPC=0.700/0.300/1.012, to the 1st vertical mixing reactor Give, in addition, obtain polycarbonate resin similarly to Example 1.The glass transition temperature of pellet is 122 DEG C.By institute Polycarbonate resin is obtained as PC2.

[Production Example 3]

With mol ratio ISB/CHDM/DPC=0.700/0.300/1.000, using as the calcium acetate monohydrate of catalyst The aqueous solution by relative to whole dihydroxy compounds 1mol turn into 1.25 μm of ol in a manner of be continuously supplied into the 1st vertical mixing Reactor, the reaction temperature of each reactor, internal pressure, holdup time are set to：1st vertical mixing reactor：188℃、 24.2kPa, 90 minutes, the 2nd vertical mixing reactor：194 DEG C, 19.9kPa, 60 minutes, the 3rd vertical mixing reactor：214 DEG C, 9.9kPa, 60 minutes, the 4th Horizontal stirring reactor：225 DEG C, 0.1kPa, 120 minutes, in extruder, by barrel zone temperature 4 barrels sets of first half are 240 DEG C, later half 6 barrels sets are 195 DEG C, screw speed is set as 225rpm, in addition, Carry out similarly to Example 1.The glass transition temperature of pellet is 122 DEG C.Using gained polycarbonate resin as PC3.

[Production Example 4]

Using by vertical mixing reactor and twin-screw extrusion mechanism into batch polymerization equipment, carry out makrolon The polymerization of resin.ISB and CHDM and DPC is set to be melted respectively in tank, by ISB with mol ratio ISB/CHDM/DPC=0.700/ 0.300/1.000 supply to the 1st vertical mixing reactor.Simultaneously, using as the aqueous solution of the cesium carbonate of catalyst with carbonic acid Caesium turns into 1.25 μm of ol mode relative to whole dihydroxy compounds 1mol, supplies to the 1st vertical mixing reactor.As anti- The process for the 1st step answered, heating tank temperature is heated to 150 DEG C, raw material is melted while stirring 15 minutes, will pressure with 40 minutes For power from atmospheric depressurized to 13.3kPa, side made heating tank temperature rise to 190 DEG C with 40 minutes, while by caused phenol take out to Outside reaction vessel.After reaction vessel entirety is kept for 15 minutes with 190 DEG C, as the process of the 2nd step, made heating tank with 30 minutes Temperature rises to 240 DEG C.It is below 0.200kPa with the 30 minutes pressure made in reaction vessel after starting to warm up after 10 minutes, Phenol caused by making distillates.After 120 minutes, after reaching defined stirring torque, stop reaction, be continuously taken out gathering from reactor Carbonate resin, resin is then directly fed to double screw extruder [Corporation Japan Steel Works' system with molten condition TEX30α].Extruder has 3 vaccum exhaust outlets, and the residual low molecular composition devolatilization in resin is removed.From the 1st exhaust outlet Nearby supply be coated with the masterbatch pellet of phosphorous acid, add phosphorous acid 0.65ppm (with phosphorus atoms for polycarbonate resin Amount is calculated as 0.2ppm), for resin, the weight ppm of water 2000 is added, water filling devolatilization is carried out, from the 3rd in the 2nd exhaust outlet nearby Exhaust outlet nearby, supplies AS2112500ppm, Irganox10101000ppm.In extruder (all 10 machine barrels), by machine barrel Temperature be set as 220 DEG C, screw speed be set as 230rpm.Resin temperature at outlet of extruder is 261 DEG C.

Pass through the polycarbonate resin of extruder then with molten condition directly by filter, after foreign body filtering, With strand form from mould discharge, water cooling, and make its solidify after, utilize rotary cutting machine carry out pellet.The vitrifying of pellet Transition temperature is 122 DEG C.Using gained polycarbonate resin as PC4.

The amount of compound shown in phenol and formula (3) that polycarbonate resin contains is concluded and is shown in table 2 below.

[table 2]

Table 2

		PC1	PC2	PC3	PC4
						Phenol content	ppm	613	527	319	1094
The content of compound shown in formula (3)	ppm	392	612	1102	1342

[embodiment 1]

Using ration feeding machine, by the parts by weight of polycarbonate resin (PC1) 100 and UVA-1 1.5 described in Production Example 1 Parts by weight are supplied to double screw extruder (Corporation Japan Steel Works TEX30 α, barrels set temperature with exhaust outlet： 240 DEG C), by filter by after foreign body filtering, discharged with strand form from mould, water cooling, and after solidifying it, using rotary Cutting machine carries out pellet.

Afterwards, by the poly carbonate resin composition with 2kg/ hours in Co., Ltd. O CS gel counter FSA films Check circuit (barrels set temperature：240 DEG C, T die heads (width 150mm, design temperature：240 DEG C), chill roll (design temperature： 105 DEG C)) in, extrusion molding is the film of 40 μm of thickness.Show the result in Table 3 below.

[embodiment 2~13, comparative example 1~5]

As described in Table 3, the thickness of film, the species of ultra-violet absorber and ultra-violet absorber are changed Amount, in addition, implements similarly to Example 1.

The film of embodiment 1~13 is that the numerical value of thickness and precision is especially small, has the film of uniform thickness, meanwhile, The amount of the film foreign matter of per unit area is also few, is especially excellent film.

On the other hand, in comparative example 1~5, the species and amount of used ultra-violet absorber are visible to think by resin The reduction of the heat resistance of composition, from caused by the roller pollution oozed out, the thickness and precision of film deteriorate, the increasing of foreign matter amount Add.

It should be noted that in comparative example 4 and comparative example 5, substantial amounts of fine foreign matter is confirmed, rather than think thin Film entirety middle-ultraviolet lamp absorbent have accumulated due to not melting, more than 150 μm of foreign matter.

[table 3]

[embodiment 14~16]

As described in Table 4, any polycarbonate resin used being changed to from PC1 in PC2, PC3 and PC4 Person, in addition, implement similarly to Example 4.

The film of embodiment 14~16 is that the numerical value of thickness and precision is especially small, has the film of uniform thickness, meanwhile, The amount of the film foreign matter of per unit area is also few, is especially excellent film.

[table 4]

Table 4

		Embodiment 4	Embodiment 14	Embodiment 15	Embodiment 16
						Use resin		PC1	PC2	PC3	PC4
Ultra-violet absorber		UVA-1	UVA-1	UVA-1	UVA-1
						Addition	Parts by weight	3	3	3	3
Thickness	μm	25	25	25	25
						Glass transition temperature	℃	120	120	120	120
The change of glass transition temperature	℃	-2	-2	-2	-2
						380nm transmissivities	%	3.2	3.2	3.2	3.2
Roller pollutes	-	○	○-	△	△-
						Film foreign matter	Individual/m2	4	5	7	10
Thickness and precision	%	3	3	5	6

[embodiment 17~19]

As described in Table 5, any polycarbonate resin used being changed to from PC1 in PC2, PC3 and PC4 Person, in addition, implement similarly to Example 6.

The film of embodiment 17~19 is that the numerical value of thickness and precision is especially small, has the film of uniform thickness, meanwhile, The amount of the film foreign matter of per unit area is also few, is especially excellent film.

[table 5]

Table 5

		Embodiment 6	Embodiment 17	Embodiment 18	Embodiment 19
						Use resin		PC1	PC2	PC3	PC4
Ultra-violet absorber		UVA-3	UVA-3	UVA-3	UVA-3
						Addition	Parts by weight	1.1	1.1	1.1	1.1
Thickness	μm	25	25	25	25
						Glass transition temperature	℃	121	121	121	121
The change of glass transition temperature	℃	-1	-1	-1	-1
						380nm transmissivities	%	3.7	3.7	3.7	3.7
Roller pollutes	-	◎	○	△	△-
						Film foreign matter	Individual/m2	2	3	7	9
Thickness and precision	%	1	2	5	6

[embodiment 20]

Using ration feeding machine, by the parts by weight of polycarbonate resin (PC1) 100 and UVA-3 1.2 described in Production Example 1 Parts by weight are supplied to double screw extruder (Corporation Japan Steel Works TEX30 α, barrels set temperature with exhaust outlet： 240 DEG C), by filter by after foreign body filtering, discharged with strand form from mould, water cooling, and after solidifying it, using rotary Cutting machine carries out pellet.

Afterwards, by the poly carbonate resin composition with 2kg/ hours in Co., Ltd. O CS gel counter FSA films Check circuit (barrels set temperature：240 DEG C, T die heads (width 150mm, design temperature：240 DEG C), chill roll (design temperature： 105 DEG C)) in, extrusion molding is the film of 50 μm of thickness.From the film be cut into length 125mm, width 50mm it is non-stretched thin Film, with the biaxial stretch-formed device of batch (-type) (ア イ ラ ンド Industrial Co., Ltd system], with rate of straining 5mm/ minutes, draft temperature 134 DEG C, carry out the fixing end uniaxial tension of 1.8 times of stretching ratio.For the transparent membrane of stretching is cut into width 4cm, length 4cm sample, using measuring difference of phases device (prince measure machine Co. Ltd. system product name " KOBRA WRXY2020 ", 23 DEG C of interior, it is 139nm when determining phase difference R548 in wavelength 548nm face.Result is concluded and is shown in table 6 below.

[table 6]

Table 6

Display rectilinearly polarized light is pasted on using the polycarbonate resin film manufactured in embodiment 20 as phase-contrast film Image display picture top layer, observe display across polarized sunglasses, be not as a result display black, and also without true Recognize the generation of rainbow pattern, be good result.

The present invention is described in detail using specific mode, but to those skilled in the art, it is aobvious and easy See, various changes and deformation can be carried out without departing from the spirit and scope in the present invention.It should be noted that The application is drawn it entirely through reference based on Japanese patent application (Patent 2015-086969) filed in 21 days April in 2015 Enter so far.

Industrial applicability

According to the present invention it is possible to provide：There is no the heat resistance of film to reduce, film caused by the material that oozes out it is muddy The problems such as bad orders of film such as the foreign matter of film turbid, from roller pollution, gear line etc., exterior quality are excellent and thin The uniformity of film thickness also excellent polycarbonate resin film.

Thus, be advantageous to cut down and be thinned using manufacturing process's loss of its Polarizer, the structure of image display device Deng.

Claims (6)

1. a kind of polycarbonate resin film, it is the polycarbonate resin film formed by poly carbonate resin composition, institute Poly carbonate resin composition is stated to contain：Include the poly- carbon of the construction unit from the dihydroxy compounds shown in following formula (1) The parts by weight of acid ester resin 100；With, relative to the parts by weight of polycarbonate resin 100 be more than 0.45 parts by weight and 7 parts by weight below Fusing point be higher than 240 DEG C of ultra-violet absorber, the poly- carbonic acid less than 300 DEG C and 5% weightless temperature for 135 DEG C The wavelength 380nm of ester resin film light transmittance is more than 0.001% and less than 15% and thickness is 5 μm~120 μm,

2. polycarbonate resin film according to claim 1, wherein, the following formula (3) in the polycarbonate resin The content of shown compound is more than 10 weight ppm and below 1200 weight ppm,

3. polycarbonate resin film according to claim 1 or 2, wherein, the ultra-violet absorber is triazine system, benzene And triazole system, quinolinone system, benzoxazole system or indoles system.

4. according to polycarbonate resin film according to any one of claims 1 to 3, phase difference is in the face at its 548nm More than 100nm and below 200nm.

5. a kind of polarisation part protective film, its be the polycarbonate resin film any one of usage right requirement 1~4 and Into.

6. a kind of poly carbonate resin composition, it contains：Include the structure from the dihydroxy compounds shown in following formula (1) The parts by weight of polycarbonate resin 100 of unit；With, relative to the parts by weight of polycarbonate resin 100 be more than 0.45 parts by weight and 7 Fusing point below parts by weight is higher than 240 DEG C of ultra-violet absorber for 135 DEG C less than 300 DEG C and 5% weightless temperature, The content of the compound shown in following formula (3) in the polycarbonate resin be more than 10 weight ppm and 1200 weight ppm with Under,